Allylic Carbon-Carbon Double Bond Directed Pd

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After that, alkene 2 (1.50 mmol) was added and the reaction mixture was stirred at ... The mixture of 2-bromoaniline (5g, 29.06 mmol) and aq. HCl (37 %, 15 mL) ...

Allylic Carbon-Carbon Double Bond Directed Pd-Catalyzed Oxidative orthoOlefination of Arenes Parthasarathy Gandeepan and Chien-Hong Cheng* Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan [email protected]

Supporting Information

Table of Contents

Page No

Experimental Section

S-2

Synthesis of Compound [d5]-1j

S-3

Synthesis of Compound [d1]-1j

S-4

Synthesis of Compound [d5]-1r

S-5

Details of Optimization Studies

S-7

Intermolecular Competition Experiments with Substituted Allyl Arenes

S-9

Intermolecular Isotope Effect for the Pd-Catalyzed Oxidative Coupling Reaction of 1j with 2a. Intramolecular Isotope Effect for the Pd-Catalyzed Oxidative Coupling Reaction of 1j with 2a. 1 H and 13C NMR and HRMS Data

S-11

S-13

References

S-26

NOE Data of Compound 3g

S-27

1

S-28

H and 13C NMR Spectra

S-12

ORTEP Diagram of 3l

S-69

X-Ray Data of 3l

S-70

S1

General. All reactions were conducted under nitrogen atmosphere on a dual-manifold Schlenk line unless otherwise mentioned and in oven-dried glass wares. All solvents were dried according to known methods and distilled prior to use.1 Starting materials alkenes were synthesized according to the literature procedures.2-3 Other reagents were commercially available and used as purchased. General Procedure for the Preparation of Alkene Derivatives 1a-1i Using Cobalt Catalyzed Head to Tail Dimerization of Styrenes.2

A seal tube initially fitted with a septum containing CoCl2(PPh3)2 (10 mol%), Zn (7.5 mmol), and PPh3 (30 mol%), was evacuated and purged with nitrogen gas three times. Vinylarene (5.00 mmol), EtOH (20 mol%) and CH3CN (5 mL) were added to the system and the reaction mixture was stirred at 80 °C for 20 h. The mixture was filtered through a short Celite pad and washed with dichloromethane several times. The filtrate was concentrated by vacuum and separated on a silica gel column using hexane/EtOAc as eluent to give the corresponding pure 1,3-diaryl-1-butenes. General Procedure for the Preparation of Alkene Derivatives 1j-1n.3

A seal tube initially fitted with a septum containing Pd(PPh3)4 (1 mol%),and boronic acid 6 mmol), was evacuated and purged with nitrogen gas three times. Allyl alcohol (5 mmol) and THF were added to the reaction system and the reaction mixture was stirred at 80 °C for 6-8 h. The mixture was filtered through a short Celite pad and washed with dichloromethane several times. The filtrate was concentrated by vacuum and separated on a silica gel column using hexane/EtOAc as eluent to give the corresponding pure prop-1-ene-1,3-diyldiarenes.

S2

General Procedure for the Palladium-Catalyzed ortho-Olefination of Allyl Arenes A seal tube containing Pd(OAc)2 (10 mol %), was evacuated and filled with dioxygen gas using an oxygen containing balloon. Then, dichloromethane (3.0 ml), styrene derivatives 1 (0.50 mmol) and trifluoroacetic acid (TFA) (4.00 mmol) were sequentially added to the system via syringe under an oxygen atmosphere. After that, alkene 2 (1.50 mmol) was added and the reaction mixture was stirred at room temperature for 36 h. When the reaction was complete, the mixture was diluted with CH2Cl2 (10 mL). The mixture was filtered through a Celite pad and the Celite pad was washed with CH2Cl2 (50 mL). The combined filtrate was concentrated and the residue was purified by column chromatography (silica gel, hexane–EtOAc) to give the corresponding pure oxidative coupling product 3. Synthesis of Compound [d5]-1j

A two-neck 500 mL flask fitted with magnetic stirring bar, and low-temperature thermometer was charged with bromobenzene-D5 (8.1 mL, 40.0 mmol) under nitrogen atmosphere. Dry THF (100 mL) was added, and the solution was cooled to -78°C. To this solution was added n-butyllithium (25.0 mL, 1.6 M, 40.0 mmol) drop wise using slow addition pump over 30 minutes. The solution was stirred at -78°C for 2 h whereupon triisopropyl borate (6.3 g, 60.0 mmol) dissolved in 10 mL of dry THF was added drop wise to the reaction system. The solution was allowed to warm to room temperature overnight. After that the reaction was quenched with dilute HCl (20%, 70 mL), and the reaction mixture was stirred for 3 h at room temperature. The resulted biphasic solution was extracted with Et2O (2 X 50 mL). The ethereal solution was washed twice with H2O and concentrated by rotary evaporation. To the crude product (viscous liquid), hexane 75 ml was added. The white (d5-phenyl)boronic acid solid precipitated in hexane was filtered and dried and used without further purification (77% isolated yield).

S3

A seal tube initially fitted with a septum containing Pd(PPh3)4 (1 mol%),and boronic acid (6 mmol), was evacuated and purged with nitrogen gas three times. Allyl alcohol (5 mmol) and THF were added to the reaction system and the reaction mixture was stirred at 80 °C for 8 h. The mixture was filtered through a short Celite pad and washed with dichloromethane several times. The filtrate was concentrated by vacuum and separated on a silica gel column using hexane/EtOAc as eluent to give the pure compound [d5]-1j. The deuterium content of [d5]-1j was observed to be more than 98% in 1H-NMR and MS spectra. Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 7.39 (d, 7.6 Hz, 2 H), 7.31 (td, J = 2 Hz, J = 8.6 Hz, 2 H), 7.21 (td, J = 1.2 Hz, J = 6.4 Hz, 1 H), 6.50-6.36 (m, 2 H), 3.59 (d, J = 6.4 Hz, 2 H);

13

C

NMR (100 MHz, CDCl3): δ 140.0 (C), 137.4 (C), 131.0 (CH), 129.2 (CH), 128.4 (2 CH), 127.0 (CH), 126.1 (2 CH), 39.2 (CH2); HRMS (EI+) calcd for C15H9D5 199.1409, found 199.1401. Synthesis of Compound [d1]-1j

The mixture of 2-bromoaniline (5g, 29.06 mmol) and aq. HCl (37 %, 15 mL) in H2O (50 mL) was cooled to 0°C, then a solution of NaNO2 (2.41 g, 34.87mmol) in H2O (50 mL) was added. The solution of KI (7.23g, 43.59 mmol) in H2O (11 mL) was added dropwise to the above solution after the solid was dissolved completely, the color of solution turned to blood-red. After addition, the mixture was stirred for 30 min at room temperature, and then heated at 70°C for another 1 h. After cooling, the solution was neutralized by slow addition of a solution of Na2S2O3 (0.43 mol/L, 20 mL), then extracted with CH2Cl2 (100 mL), the organic phase was washed with H2O and dried over anhydrous MgSO4, After filtration, the solvents was removed under reduced pressure and the residue was distilled to afford product as a paleS4

yellow liquid (3.85 g, yield: 77 %). 1H NMR (CDCl3, 500MHz): δ 7.88-7.86(dd, J = 8.0Hz, J = 1.4Hz 1H); 7.64-7.62(dd, J = 8.0 Hz, J=1.4 Hz, 1H); 7.30-7.20 (td, J = 7.9 Hz, J =1.4Hz 1H); 7.02-6.99 (td, J = 7.8 Hz ,J = 1.4 Hz ,1H). To a solution of 1-bromo-2-iodobenzene (5 g, 17.7 mmol) in a mixture of THF and Et2O (120 mL, 1:1) at -78 °C was added dropwise isopropyl magnesium chloride (2 M in THF, 9.0 mL, 18.0 mmol). The mixture was stirred at that temperature for 2 h and then, CD3OD (2 g, 55.5 mmol) was added. The solution was slowly warmed to room temperature. HCl (10% aq., 100 mL) was added and the resulting mixture was stirred for 30 min. at room temperature. The aqueous layer was extracted with Et2O (3 x 30 mL). The pure 2-deuterio bromobenzene was obtained by distillation. 98.5% deuterium incorporation was observed in 1H and mass spectrum data’s. Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 7.5 (d, J = 7.6 Hz, 1 H), 7.32-7.22 (m, 3 H); 13

C NMR (100 MHz, CDCl3): δ 131.7 (CH), 130.2 (CH), 130.1 (CH), 127.1 (CH), 122.6 (C); HRMS

(EI+) calcd for C6H4DBr 156.9637, found 156.9634. Compound [d1]-1j was prepared from 2-deutrio bromobenzene using the same procedure as [d5]-1j. Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 7.43 (d, J = 8.0 Hz, 2 H) 7.40-7.25 (m, 7 H), 6.53 (d, J = 15.6 Hz, 1 H), 6.46-6.39 (m, 1 H), 3.62 (d, J = 6.8 Hz, 2 H); 13C NMR (100 MHz, CDCl3): δ 140.0 (C), 137.4 (C), 131.0 (CH), 129.1 (CH), 128.6 (CH), 128.4 (3 CH), 128.3 (CH), 127.0 (CH), 126.1 (CH), 126.0 (2 CH), 39.3 (CH2); HRMS (EI+) calcd for C15H13D 195.1158, found 195.1154. Synthesis of Compound [d5]-1r

Compound [d5]-1r was synthesised using a modified literature procedure4: A 50-mL two-neck roundbottom flask, fitted with a reflux condenser, was charged with Sc(OTf)3 (0.250 g, 0.5 mmol) and C6D6 (5.0 mL). To the mixture was added (E)-hex-2-en-1-ol (290.0 mg, 5.0 mmol) at ambient temperature. The mixture was vigorously stirred at the reflux temperature for 2 h, then treated with H2O, and extracted with S5

diethyl ether (10 mL) three times. The combined extracts were dried over MgSO4. Then the crude product was purified on silica gel column using hexane/EA as eluent. Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 5.54-5.51 (m, 2 H), 3.32 (d, J = 6.0 Hz, 2 H), 2.01-1.96 (m, 2 H), 1.41-1.35 (m, 2 H), 0.88 (t, J = 7.6 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 131.8 (CH), 131.6 (C), 128.8 (CH), 38.9 (CH2), 34.5 (CH2), 22.5 (CH2), 13.6 (CH3); HRMS (EI+) calcd for C12H11D5 165.1566, found 165.1565. 2-Methyl 3-(2-(4-chloro-3-ethylhex-3-en-2-yl)phenyl)acrylate

The compound 1q was prepared using the slightly modified literature procedure5. To a stirred solution of anhydrous ferric chloride (0.8 mmol) and 1-phenylethanol (2 mmol) in dry dichloromethane (6 mL) was added hex-3-yne (2 mmol). The reaction mixture was stirred vigorously at room temperature, keeping the container tightly closed with a glass stopper. After completion of the reaction (checked by TLC), dichloromethane was evaporated under reduced pressure and the residue was purified by silica-gel column chromatography (hexane/EA) to afford a mixture of E and Z isomers of desired product 3a (E:Z, 2:1) as a colourless liquid in 73% yield.

S6

Table 1. Optimization Studies for the Pd-Catalyzed ortho Alkenation of Styrene Dimer 1a.[a]

Entry

Pd source

Oxidant/equiv

Additive /equiv

Solvent

Temp °C /Time h

3a Yield%[b]

1

Pd(OAc)2

Ag2O/2

-

TFA

80/24

15

2

Pd(OAc)2

Ag2O/2

-

TFA

50/24

18

3

Pd(OAc)2

Ag2CO3/2

-

TFA

50/24

trace

4

Pd(OAc)2

AgOAc

-

TFA

50/24

7

5

Pd(OAc)2

Cu(OAc)2/2

-

TFA

80/24

17

6

Pd(OAc)2

K2S2O8/2

-

TFA

80/24

-

7

Pd(OAc)2

BQ/2

-

TFA

80/24

-

8

Pd(OAc)2

Ag2O/2

-

DCE

80/24

-

9

Pd(OAc)2

Ag2O/2

-

CH3COOH

80/24

-

10

Pd(OAc)2

Ag2O/2

-

Dioxane

80/24

-

11

Pd(OAc)2

Ag2O/2

-

DMF

80/24

-

12

Pd(OAc)2

Ag2O/2

-

DMSO

80/24

-

13

Pd(OAc)2

Ag2O/2

-

Toluene

80/24

-

14

Pd(OAc)2

Ag2O/2

-

TFA

25/24

22

15

Pd(OAc)2

Ag2O/2

-

DCE/TFA (1:1)

25/24

27

16

Pd(OAc)2

Ag2O/2

-

DCM/TFA(1:1)

25/24

32

17

Pd(OAc)2

Cu(OAc)2/2

-

DCM/TFA(1:1)

25/24

12

18

Pd(OAc)2

Cu(OAc)2/1/O2

-

DCM/TFA(1:1)

25/24

27

20

Pd(OAc)2

O2

-

DCM/TFA(1:1)

25/24

32

21

Pd(OAc)2

O2

TFA (10)

DCM

25/24

47

22

Pd(OAc)2

O2

TFA (5)

DCM

25/24

60

23

Pd(OAc)2

O2

TFA (8)

DCM

25/24

65

24

Pd(OAc)2

O2

TFA (8)

DCM

25/36

71

25

Pd(OAc)2

O2

TFA (8)

DCM

25/24

80[c]

S7

26

Pd(OAc)2

O2

TFA (8)

DCM

25/36

94[c]

27

Pd(OAc)2

O2

TFA (8)

DCE

25/36

63

28

Pd(OAc)2

O2

TFA (8)

DCE

50/24

51

29

Pd(OAc)2

Ag2O/2

TFA (8)

DCM

25/24

11

30

Pd(OAc)2

Cu(OAc)2/1/O2

TFA (8)

DCM

25/24

33

31

Pd(OAc)2

Cu(OAc)2/2

TFA (8)

DCM

25/24

16

32

Pd(OAc)2

O2

AcOH (8)

DCM

25/36

trace

33

Pd(OAc)2

O2

PivOH (8)

DCM

25/36

12

34

Pd(OAc)2

O2

TFA (8)

AcOH

25/36

trace

35

Pd(OAc)2

O2

TFA (8)

DMSO

25/36

-

36

Pd(OAc)2

O2

TFA (8)

Dioxane

25/36

-

37

Pd(OAc)2

O2

TFA (8)

DMF

25/36

-

38

PdCl2

O2

TFA (8)

DCM

25/36

-

39

PdCl2(PPh3)2

O2

TFA (8)

DCM

25/36

-

40

PdCl2(CH3CN)2

O2

TFA (8)

DCM

25/36

16

41

Pd(OAc)2

O2

-

DCM

25/36

-

42

Pd(OAc)2

-

TFA

DCM

25/36

6

43

-

O2

TFA

DCM

25/36

-

44

Pd(OAc)2

O2

-

TFA

25/36

17

[a] Unless otherwise mentioned, all reactions were carried out using styrene derivatives 1a (0.5 mmol), butyl acrylate 2a (1.0 mmol). [b] Yields were determined by the 1H NMR integration method using mesitylene as the internal standard. [c] Butyl acrylate 2a (1.5 mmol) was used.

S8

Intermolecular Competition Experiments between Two Substituted Allyl Arenes: Competition Experiments of Substituted Allyl Arenes 1c and 1d with 2a

A seal tube containing Pd(OAc)2 (22 mg, 0.1 mmol) was evacuated and filled with dioxygen gas using an oxygen containing balloon. Substituted allyl arene 1c (160 mg, 0.5 mmol) and 1d (122 mg, 0.5 mmol) in DCM (6 mL) and then TFA (900 mg, 8.0 mmol) were added to the system via syringe under an oxygen atmosphere. After that, alkene 2a (256 mg, 2.0 mmol) was added and the reaction mixture was stirred at room temperature for 15 h. The mixture was then diluted with CH2Cl2 (10 mL) and was filtered through a Celite pad. The Celite pad was washed with CH2Cl2 (50 mL) and the combined filtrate was concentrated. The yields of the products were determined by NMR integration using mesitylene as the internal standard. Intermolecular Competition Experiments of Substituted Allyl Arenes 1n and 1o with 2a CO2n-Bu

2a (2.0 mmol) Pd(OAc)2 (0.1 mmol) 1n (0.5 mmol) +

TFA (8.0 mmol)

3na (37%) CO2n-Bu

O2 (1 atm) DCM (6 mL), rt, 15 h 1o (0.5 mmol)

F 3oa (23%)

F

A seal tube containing Pd(OAc)2 (22 mg, 0.1 mmol), was evacuated and filled with dioxygen gas using oxygen containing balloon. Substituted allyl arenes 1n (125 mg, 0.5 mmol) and 1o (106 mg, 0.5 S9

mmol) in DCM (6 mL) and then TFA (900 mg, 8.0 mmol) were added to the system via syringe under an oxygen atmosphere. After that, alkene 2a (256 mg, 2.0 mmol) was added and the reaction mixture was stirred at room temperature for 15 h. The mixture was then diluted with CH2Cl2 (10 mL) and was filtered through a Celite pad. The Celite pad was washed with CH2Cl2 (50 mL) and the combined filtrate was concentrated. The yields of the products were determined by NMR integration using mesitylene as the internal standard. Intermolecular Competition Experiments with Substituted Allyl Arenes 1j and 1n with 2a CO2n-Bu

2a (2.0 mmol) Pd(OAc)2 (0.1 mmol) 1j (0.5 mmol) +

TFA (8.0 mmol)

3ja (21%) CO2n-Bu

O2 (1 atm) DCM (6 mL), rt, 15 h 1r (0.5 mmol) 3ra (34%)

A seal tube containing Pd(OAc)2 (22 mg, 0.1 mmol) was evacuated and filled with dioxygen gas using an oxygen containing balloon. Substituted allyl arene 1j (97 mg, 0.5 mmol) and 1r (80 mg, 0.5 mmol) in DCM (6 mL) and then TFA (900 mg, 8.0 mmol) were added to the system via syringe. After that, alkene 2a (256 mg, 2.0 mmol) was added and the reaction mixture was stirred at room temperature for 15 h under an oxygen atmosphere. The mixture was then diluted with CH2Cl2 (10 mL) and was filtered through a Celite pad. The Celite pad was washed with CH2Cl2 (50 mL) and the combined filtrate was concentrated. The yields of the products were determined by NMR integration using mesitylene as the internal standard. Conclusion of the competition experiments shown above The results of these three sets of reaction revealed that substrates 1c, 1n and 1r with an electronricher substituent on the allylic arene ring or on the C-C double bond gave a higher product yield than 1o,

S10

1j and 1d, respectively. The observations support the coordination of C-C double to Pd(II) and an electrophilic C-H activation during the reaction (see proposed mechanism, Scheme 2). Intermolecular Kinetic Isotope Effect of the Pd-Catalyzed Oxidative Coupling Reaction of 1j with 2a.

A seal tube containing Pd(OAc)2 (22 mg, 0.1 mmol) was evacuated and filled with dioxygen gas using an oxygen containing balloon. Substituted allyl arene 1j (97 mg, 0.5mmol) and [d5]-1j (100 mg, 0.5 mmol) in DCM (6 mL) and then TFA (900 mg, 8.0 mmol) were added to the system via syringe under an oxygen atmosphere. After that, alkene 2a (256 mg, 2.0 mmol) was added and the reaction mixture was stirred at room temperature for 15 h. At the end of the reaction, the mixture was diluted with CH2Cl2 (10 mL). The mixture was filtered through a Celite pad and the Celite pad was washed with CH2Cl2 (50 mL). The filtrate was concentrated and the residue was purified on a silica gel column using EtOAc/n-hexane as eluent to afford 3ja and [d4]-3ja product mixture (144 mg, 45%) as a colourless oil. The above experiment was repeated two times and the ratio of two compounds was determined by 1

H NMR (integration of a doublet at δ 7.61 for 1 H of 3ja and integration of doublet at δ 8.05 for 1 H of

3ja and [d4]-3ja to gave intermolecular kinetic isotopic effect (KIE) kH/kD = 1.64 (1.62, in the second run). The KIE determined by HRMS was 1.58.

S11

Intramolecular Kinetic Isotope Effect of the Pd-Catalyzed Oxidative Coupling Reaction of [d1]-1j with 2a.

A seal tube containing Pd(OAc)2 (10 mol %), was evacuated and filled with dioxygen gas using an oxygen containing balloon. Then, styrene derivatives [d1]-1j (0.50 mmol) in dichloromethane (3.0 ml), and trifluoroacetic acid (TFA) (4.00 mmol) were sequentially added to the system via syringe under an oxygen atmosphere. After that, alkene 2a (1.50 mmol) was added and the reaction mixture was stirred at room temperature for 15 h. At the end of the reaction, the mixture was diluted with CH2Cl2 (10 mL). The mixture was filtered through a Celite pad and the Celite pad was washed with CH2Cl2 (50 mL). The filtrate was concentrated and the residue was purified on a silica gel column using EtOAc/n-hexane as eluent to afford product mixture 3ja + [d1]-3ja in 42% yield. An intramolecular kinetic isotopic effect kH/kD = 3.7 determined by HRMS was obtained.

S12

The spectral data and a copy of 1H and 13C NMR spectra of all compounds are listed below. (E)-Butyl 3-(2-((E)-4-phenylbut-3-en-2-yl)phenyl)acrylate (3a) CO2n-Bu

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.15 (d, J = 15.6 Hz, 1 H) 7.54 (d, J = 7.6 Hz, 1 H), 7.37-7.35 (m, 3 H), 7.31-7.17 (m, 5 H), 6.38-6.32 (m, 3 H), 4.20 (t, J = 6.8 Hz, 2 H), 4.06-4.04 (m, 1 H), 1.71-1.63 (m, 2 H), 1.47-1.25 (m, 5 H), 0.95 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.9 (ester carbonyl), 144.6 (C), 142.5 (CH), 137.3 (C), 134.1 (CH), 133.0 (C), 130.1 (CH), 129.2 (CH), 128.4 (2 CH), 127.1 (2 CH), 126.9 (CH), 126.5 (CH), 126.1 (2 CH), 120.2 (CH), 64.4 (CH2), 37.8 (CH), 30.7 (CH2), 20.9 (CH3), 19.1 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C23H26O2 334.1933, found 334.1937; IR (KBr): 2969, 2931, 1714, 1628, and 1023 cm-1 (E)-Ethyl 3-(2-((E)-4-phenylbut-3-en-2-yl)phenyl)acrylate (3b)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.16 (d, J = 16.0 Hz, 1 H), 7.54 (d, J = 7.6 Hz, 1 H), 7.38-7.17 (m, 8 H), 6.43-6.32 (m, 3 H), 4.26 (q, J = 7.2 Hz, 2 H), 4.07-4.03 (m, 1 H), 1.46 (d, J = 7.2 Hz, 3 H), 1.34 (t, J = 7.2 Hz. 3 H); 13C NMR (100 MHz, CDCl3): δ 166.8 (ester carbonyl), 144.6 (C), 142.2 (CH), 137.3 (C), 134.1 (CH), 132.9 (C), 130.1 (CH), 129.2 (CH), 128.4 (2 CH), 127.1 (2 CH), 126.9 (CH), 126.5 (CH), 126.1 (2 CH), 120.2 (CH), 60.4 (CH2), 37.8 (CH), 20.9 (CH3), 14.2 (CH3); HRMS (EI+) calcd for C21H22O2 306.1620, found 306.1624; IR (KBr): 2969, 2931, 1712, 1635, 1481, 1450, 1311,1172, 1033, 971 and 717 cm-1 (E)-Methyl 3-(2-((E)-4-phenylbut-3-en-2-yl)phenyl)acrylate (3c)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.19 (d, J = 16.0 Hz, 1 H), 7.56 (d, J = 8.0 Hz, 1 H), 7.39-7.19 (m, 8 H), 6.44-6.35 (m, 3 H), 4.09-4.06 (m, 1 H), 3.81 (s, 3 H), 1.48 (d, J = 6.8 Hz, 3 H); 13 C NMR (100 MHz, CDCl3): δ 167.2 (ester carbonyl), 144.6 (C), 142.4 (CH), 137.2 (C), 134.0 (CH), S13

132.8 (C), 130.2 (CH), 129.2 (CH), 128.4 (2 CH), 127.1 (2 CH), 126.9 (CH), 126.5 (CH), 126.1 (2 CH), 119.7 (CH), 51.6 (CH3), 37.7 (CH), 20.9 (CH3); HRMS (EI+) calcd for C20H20O2 292.1463, found 292.1471; IR (KBr): 1712, 1635, 1442, 1319, 1172 and 586 cm-1 (E)-tert-Butyl 3-(2-((E)-4-phenylbut-3-en-2-yl)phenyl)acrylate (3d)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.05 (d, J = 16.0 Hz, 1 H), 7.52 (d, J = 7.5 Hz, 1 H), 7.34-7.16 (m, 8 H), 6.41-6.32 (m, 2 H), 6.25 (d, J = 15.0 Hz, 1 H), 4.04-4.02 (m, 1 H), 1.57 (s, 9 H), 1.44 (d, J = 7.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.2 (ester carbonyl), 144.5 (C), 141.2 (CH), 137.3 (C), 134.2 (CH), 133 1 (C), 129.9 (CH), 129.1 (CH), 128.4 (2 CH), 127.1 (2 CH), 126.9 (CH), 126.5 (CH), 126.1 (2 CH), 122.0 (CH), 80.5 (C), 37.8 (CH), 28.1 (3 CH3), 20.9 (CH3); HRMS (EI+) calcd for C23H26O2 334.1933, found 334.1938; IR (KBr): 2969, 2931, 1704, 1627, 1319 and 1149 cm-1 (E)-Cyclohexyl 3-(2-((E)-4-phenylbut-3-en-2-yl)phenyl)acrylate (3e)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.15 (d, J = 15.6 Hz, 1 H), 7.54 (d, J = 7.6 Hz, 1 H), 7.37-7.20 (m, 8 H), 6.43-6.39 (m, 3 H), 4.91-4.85 (m, 1 H), 4.07-4.04 (m, 1 H), 2.03-1.25 (m, 13 H); 13 C NMR (100 MHz, CDCl3): δ 166.3 (ester carbonyl), 144.5 (C), 141.9 (CH), 137.2 (C), 134.2 (CH), 133.1 (C), 130.0 (CH), 129.1 (CH), 128.4 (2 CH), 127.1 (2 CH), 126.9 (CH), 126.5 (CH), 126.1 (2 CH), 120.8 (CH), 72.6 (CH), 37.9 (CH), 31.6 (CH2), 31.5 (CH2), 25.3 (CH2), 23.7 (CH2), 23.6 (CH2), 20.9 (CH3); HRMS (EI+) calcd for C25H28O2 360.2089, found 360.2085; IR (KBr): 2939, 1712, 1635, 1450, 1311and 917 cm-1 (E)-Benzyl 3-(2-((E)-4-phenylbut-3-en-2-yl)phenyl)acrylate (3f)

S14

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.29 (d, J = 15.6 Hz, 1 H), 7.60 (d, J = 7.6 Hz, 1 H), 7.49-7.25 (m, 11 H), 6.48-6.42 (m, 3 H), 5.32 (s, 2 H), 4.13-4.10 (m, 1 H), 1.52 (d, J = 7.2 Hz, 3 H); 13 C NMR (100 MHz, CDCl3): δ 166.6 (ester carbonyl), 144.6 (C), 142.8 (CH), 137.2 (C), 136.0 (C), 134.1 (CH), 132.8 (C), 130.2 (CH), 129.2 (CH), 128.5 (2 CH), 128.4 (2 CH), 128.1 (2 CH), 127.1 (CH), 127.0 (CH), 126.9 (CH), 126.5 (CH), 126.1 (CH), 126.0 (2 CH), 119.7 (CH), 66.2 (CH2), 37.8 (CH), 20.8 (CH3); HRMS (EI+) calcd for C26H24O2 368.1776, found 368.1774; IR (KBr): 3031, 2962, 1712, 1635, 1488, 1450, 1311, 1164 and 570 cm-1 (E)-3-(2-((E)-4-Phenylbut-3-en-2-yl)phenyl)acrylic acid (3g)

White solid; m.p. 99-100 °C; 1H NMR (400 MHz, CDCl3): δ 8.34 (d, J = 15.6 Hz, 1 H), 7.62 (d, J = 7.6 Hz, 1 H), 7.44-7.27 (m, 7 H), 7.23 (t, J = 6.8 Hz, 1 H), 6.47-6.40 (m, 3 H), 4.12-4.09 (m, 1 H), 1.52 (d, J = 6.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 172.4 (acid carbonyl), 144.9 (C), 144.6 (CH), 137.3 (C), 134.0 (CH), 132.5 (C), 130.6 (CH), 129.3 (CH), 128.4 (2 CH), 127.2 (CH), 127.1 (2 CH), 126.6 (CH), 126.1 (2 CH), 119.2 (CH), 37.8 (CH), 20.9 (CH3); HRMS (EI+) calcd for C19H18O2 278.1307, found 278.1311; IR (KBr):2969, 2360, 1689, 1627, 1311 and 971 cm-1 (E)-Methyl 2-(2-(4-phenylbut-3-en-2-yl)benzyl)acrylate (3h)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 7.35-7.12 (m, 9 H), 6.35-6.34 (m, 2 H), 6.27 (d, J = 1.6 Hz, 1 H), 5.21 (d, J = 1.2 Hz, 1 H), 3.88-3.61 (m, 6 H), 1.42 (d, J = 7.2 Hz, 3 H); 13C NMR (150 MHz, CDCl3): δ 167.4 (ester carbonyl), 143.9 (C), 140.0 (C), 137.5 (C), 135.4 (C), 134.9 (CH), 130.5 (CH), 128.4 (3 CH), 127.1 (2 CH), 126.9 (CH), 126.2 (CH), 126.1 (CH2), 126.0 (2 CH), 51.9 (CH3), 37.5 (CH), 34.6 (CH2), 21.1 (CH3); HRMS (EI+) calcd for C21H22O2 306.1620, found 306.1625; IR (KBr): 3069, 2969, 1712, 1638 and 1327 cm-1 (E)-3-(2-(4-Phenylbut-3-en-2-yl)benzyl)furan-2(5H)-one (3i)

S15

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 7.36 (d, J = 7.6 Hz, 1 H), 7.32-7.23 (m, 5 H), 7.217.18 (m, 3 H), 6.72 (t, J = 2.0 Hz, 1 H), 6.34-6.24 (m, 2 H), 4.71-4.58 (m, 2 H), 3.75-3.63 (m, 3 H), 1.43 (d, J = 6.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 167.6 (ester carbonyl), 145.9 (CH), 143.4 (C), 137.2 (C), 134.8 (C), 134.7 (CH), 134.2 (C), 130.4 (CH), 128.8 (CH), 128.4 (2 CH), 127.5 (CH), 127.2 (CH), 127.1 (CH), 126.5 (CH), 125.9 (2 CH), 70.2 (CH2), 38.0 (CH), 29.1 (CH2), 21.3 (CH3); ); HRMS (EI+) calcd for C21H20O2 304.1463, found 304.1468; IR (KBr): 2360, 2331, 1751, 1488, 1450, 1064 and 532 cm-1 (E)-3-(2-((E)-4-Phenylbut-3-en-2-yl)phenyl)acrylamide (3j) CONH2

White solid, m.p 106-107 °C; 1H NMR (500 MHz, CDCl3): δ 8.10 (d, J = 15.5 Hz, 1 H), 7.49 (d, J = 8.0 Hz, 1 H), 7.35-7.15 (m, 8 H), 6.39-6.30 (m, 3 H), 5.77 (s, 1 H), 5.64 (s, 1 H), 4.11-4.03 (m, 1 H), 1.43 (d, J = 7.0 Hz, 3 H); 13C NMR (125 MHz, CDCl3): δ 167.6 (amide carbonyl), 144.7 (C), 140.3 (CH), 137.3 (C), 134.2 (CH), 133.1 (C), 129.9 (CH), 129.1 (CH), 128.4 (2 CH), 127.2 (CH), 127.1 (CH), 126.4 (2 CH), 126.1 (2 CH), 121.6 (CH), 37.7 (CH), 21.0 (CH3); HRMS (EI+) calcd for C19H19NO 277.1467, found 277.1460; IR (KBr): 2839, 1658, 1600, 1509, 1259, 1167 and 1023 cm-1 (E)-N,N-Dimethyl-3-(2-((E)-4-phenylbut-3-en-2-yl)phenyl)acrylamide (3k)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.14 (d, J = 15.2 Hz, 1 H), 7.53 (d, J = 7.6 Hz, 1 H), 7.36-7.16 (m, 8 H), 6.77 (d, J = 15.2 Hz, 1 H), 6.44-6.35 (m, 2 H), 4.13-4.09 (m, 1 H), 3.13 (s, 3 H), 3.07 (s, 3 H), 1.46 (d, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.6 (amide carbonyl), 144.4 (C), 140.2 (CH), 137.3 (C), 134.1 (CH), 133.9 (C), 129.4 (CH), 128.9 (CH), 128.3 (2 CH), 126.9 (2 CH), 126.7 (CH), 126.2 (CH), 126.0 (2 CH), 119.6 (CH), 37.6 (CH), 37.2 (CH3), 35.7 (CH3), 20.9 (CH3); HRMS (EI+) calcd for C21H23NO 305.1780, found 305.1772; IR (KBr): 3054, 2931, 1643, 1604, 1488, 1396, 1265, 717 and 647cm-1 S16

(E)-N-Benzyl-3-(2-((E)-4-phenylbut-3-en-2-yl)phenyl)acrylamide (3l)

White solid, m.p 117-119 °C; 1H NMR (400 MHz, CDCl3): δ 8.16 (dd, J = 2.0 Hz, J = 15.2 Hz, 1 H), 7.49 (d, J = 7.2 Hz, 1 H), 7.35-7.19 (m, 13 H), 6.39-6.31 (m, 3 H), 4.55 (dd, J = 2.0 Hz, J = 6.0 Hz, 2 H), 4.11-4.07 (m, 1 H), 1.45 (d, J = 4.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 165.6 (amide carbonyl), 144.6 (C), 139.1 (CH), 138.1 (C), 137.3 (C), 134.2 (CH), 133.3 (C), 129.6 (CH), 129.0 (CH), 128.6 (2 CH), 128.3 (2 CH), 127.8 (2 CH), 127.4 (CH), 127.1 (CH), 127.0 (CH), 126.6 (CH), 126.3 (CH), 126.1 (2 CH), 122.6 (CH), 43.7 (CH2), 37.6 (CH), 20.9 (CH3); HRMS (EI+) calcd for C26H25NO 367.1936, found 367.1936; IR (KBr): 3062, 2964, 1652, 1611, 1387 and 575 cm-1 (E)-3-(2-((E)-4-Phenylbut-3-en-2-yl)phenyl)acrylonitrile (3m)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 7.87 (d, J = 16.4 Hz, 1 H), 7.45 (d, J = 8.0 Hz, 1 H), 7.41 (d, J = 7.6 Hz, 1 H), 7.36-7.20 (m, 7 H), 6.35 (d, J = 1.6 Hz, 2 H), 5.79 (d, J = 16.4 Hz, 1 H), 3.94-3.91 (m, 1 H), 1.47 (d, J = 6.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 148.6 (CH), 144.2 (C), 137.0 (C), 133.6 (CH), 132.2 (C), 131.1 (CH), 129.6 (CH), 128.5 (2 CH), 127.4 (CH), 127.3 (CH), 126.8 (CH), 126.2 (CH), 126.1 (2 CH), 118.1(C), 98.2 (CH), 38.0 (CH), 20.9 (CH3); HRMS (EI+) calcd for C19H17N 259.1361, found 259.1360; IR (KBr): 3023, 2969, 2923, 2221, 1612, 1488, 1450, 1265, 964 and 809 cm-1 1-((E)-4-Phenylbut-3-en-2-yl)-2-((E)-2-(phenylsulfonyl)vinyl)benzene (3n)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.15 (d, J = 15.5 Hz, 1 H), 7.82 (d, J = 8.5 Hz, 1 H), 7.51 (t, J = 7.5 Hz, 1 H), 7.44 (d, J = 8.5 Hz, 1 H), 7.38-7.29 (m, 6 H), 7.28 (t, J = 7.5 Hz, 2 H), 7.237.19 (m, 2 H), 6.73 (d, J = 15.5 Hz, 1 H), 6.39-6.27 (m, 2 H), 4.07-4.01 (m, 1 H), 1.49 (d, J = 6.5 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 144.9 (C), 140.4 (C), 140.1 (CH), 137.0 (C), 134.0 (CH), 133.2 (CH), 131.1 (CH), 130.9 (C), 129.5 (CH) 129.2 (2 CH), 128.6 (CH), 128.5 (2 CH), 127.5 (2 CH), 127.3 S17

(CH), 127.2 (CH), 127.1 (CH), 126.7 (CH), 126.2 (2 CH), 38.3 (CH), 20.6 (CH3); HRMS (EI+) calcd for C24H22O2S 374.1341, found 374.1339; IR (KBr): 3062, 2969, 1604, 1450, 1303, 1149, 971 and 532 cm-1 (E)-Butyl 3-(5-methyl-2-((E)-4-p-tolylbut-3-en-2-yl)phenyl)acrylate (3ba)

Colourless oily liquid; 1H NMR (500 MHz, CDCl3): δ 8.12 (d, J = 16.0 Hz, 1 H), 7.36 (s, 1 H), 7.23-7.20 (m, 3 H), 7.16 (d, J = 8.5 Hz, 1 H), 7.08 (d, J = 8.0 Hz, 2 H), 6.36-6.26 (m, 3 H), 4.20 (t, J = 6.5 Hz, 2 H), 4.02-3.97 (m, 1 H), 1.78-1.65 (m, 2 H), 1.46-1.39 (m, 5 H), 0.95 (t, J = 7.5 Hz, 3 H); 13C NMR (125 MHz, CDCl3): δ 167.0 (ester carbonyl), 142.3 (CH), 141.9 (C), 136.8 (C), 135.9 (C), 134.6 (C), 133.3 (CH), 132.7 (C), 131.0 (CH), 129.1 (2 CH), 128.8 (CH), 127.4 (CH), 127.1 (CH), 126.0 (2 CH), 119.9 (CH), 119.8 (CH), 64.3 (CH2), 37.4 (CH), 30.7 (CH2), 21.0 (CH3), 20.9 (CH3), 19.1 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C25H30O2 362.2246, found 362.2242; IR (KBr): 2962, 1712, 1635, 1457, 1311, 1172 and 971 cm-1 (E)-Butyl 3-(5-tert-butyl-2-((E)-4-(4-tert-butylphenyl)but-3-en-2-yl)phenyl)acrylate (3ca)

Colourless oily liquid; 1H NMR (500 MHz, CDCl3): δ 8.14 (d, J = 15.5 Hz, 1 H), 7.52 (s, 1 H), 7.35 (dd, J = 2.5 Hz, J = 8.5 Hz, 1 H), 7.29-7.22 (m, 5 H), 6.39-6.27 (m, 3 H), 4.19 (t, J = 7.5 Hz, 2 H), 4.01-3.96 (m, 1 H), 1.70-1.64 (m, 2 H), 1.46-1.38 (m, 5 H), 1.30 (s, 9 H), 1.29 (s, 9 H), 0.94 (t, J = 8.0 Hz, 3 H); 13C NMR (125 MHz, CDCl3): δ 167.1 (ester carbonyl), 150.1 (C), 149.2 (CH), 141.9 (2 C), 134.6 (C), 133.6 (CH), 132.4 (C), 128.6 (CH), 127.4 (CH), 126.9 (CH), 125.8 (2 CH), 125.3 (2 CH), 123.6 (CH), 119.6 (CH), 64.3 (CH2), 37.5 (CH), 34.4 (2 C), 31.2 (6 CH3), 30.9 (CH2), 20.9 (CH3), 19.2 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C31H42O2 446.3185, found 446.3166; IR (KBr): 2962, 2360, 1712, 1635, 1172 and 578 cm-1 (E)-Butyl 3-(5-fluoro-2-((E)-4-(4-fluorophenyl)but-3-en-2-yl)phenyl)acrylate (3da)

S18

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.07 (d, J = 15.6 Hz, 1 H), 7.31-7.22 (m, 4 H), 7.05 (td, J = 2.8 Hz, J = 8.4 Hz, 1 H), 6.96 (t, J = 6.8 Hz, 2 H), 6.35-6.21 (m, 3 H), 4.21 (t, J = 6.8 Hz, 2 H), 4.02-3.96 (m, 1 H), 1.72-1.65 (m, 2 H), 1.49-1.38 (m, 5 H), 0.96 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.6 (ester carbonyl), 162.9 (d, JC-F = 339.6 Hz, C), 160.4 (d, JC-F = 333.6 Hz, C), 141.0 (d, JC-F = 8.8 Hz, CH), 140.2 (d, JC-F = 11.6 Hz, C), 134.8 (d, JC-F = 29.2 Hz, C), 133.7 (d, JC-F = 5.6 Hz, CH), 133.3 (d, JC-F = 11.6 Hz, C), 128.8 (d, JC-F = 32.0 Hz, CH), 128.2 (CH), 127.6 (d, JC-F = 32.0 Hz, 2 CH), 121.3 (CH), 116.9 (d, JC-F = 82.0 Hz, CH), 115.3 (d, JC-F = 84.8 Hz, 2 CH), 113.2 (d, JC-F = 84.8 Hz, CH), 64.5 (CH2), 37.3 (CH), 30.7 (CH2), 20.9 (CH2), 19.1 (CH2), 13.6 (CH3); HRMS (EI+) calcd for C23H24F2O2 370.1744, found 370.1744; IR (KBr): 2962, 1712, 1635, 971 and 532 cm-1 (E)-Butyl 3-(4-((E)-4-(biphenyl-4-yl)but-3-en-2-yl)biphenyl-3-yl)acrylate (3ea)

Colourless oil ; 1H NMR (400 MHz, CDCl3): δ 8.22 (d, J = 16.0 Hz, 1 H), 7.78 (s, 1 H), 7.61-7.33 (m, 16 H), 6.51-6.41 (m, 3 H), 4.23 (t, J = 6.8 Hz, 2 H), 4.15-4.08 (m, 1 H), 1.74-1.67 (m, 2 H), 1.53 (d, J = 7.2 Hz, 3 H), 1.50-1.40 (m, 2 H), 0.97 (t, J = 7.2 H, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.9 (ester carbonyl), 143.6 (C), 142.2 (CH), 140.7 (C), 140.3 (C), 139.9 (C), 139.5 (C), 136.4 (C), 134.2 (CH), 133.4 (C), 128.8 (4 CH), 128.7 (2 CH), 127.7 (CH), 127.4 (CH), 127.1 (3 CH), 126.9 (2 CH), 126.8 (2 CH), 126.6 (2 CH), 125.6 (CH), 120.6 (CH), 64.4 (CH2), 37.8 (CH), 30.7 (CH2), 20.9 (CH3), 19.2 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C35H34O2 486.2559, found 486.2565; IR (KBr): 2962, 2360, 1712, 1635, 1172 and 971 cm-1 (E)-Butyl 3-(5-methoxy-2-((E)-4-(4-methoxyphenyl)but-3-en-2-yl)phenyl)acrylate (3fa) CO2n-Bu

O

O

Colourless oily liquid; 1H NMR (500 MHz, CDCl3): δ 8.09 (d, J = 16.0 Hz, 1 H), 7.25-7.20 (m, 3 H), 7.03 (s, 1 H), 6.89 (dd, J = 2.0 Hz, J = 11.0 Hz, 1 H), 6.79 (d, J = 9.0 Hz, 2 H), 6.31-6.15 (m, 3 H), 4.18 (t, J = 7.5 Hz, 2 H), 3.96-3.91 (m, 1 H), 3.79 (s, 3 H), 3.76 (s, 3 H), 1.69-1.63 (m, 2 H), 1.43-1.39 (m, 5 H), 0.93 (t, J = 7.0 Hz, 3 H); 13C NMR (125 MHz, CDCl3): δ 166.9 (ester carbonyl), 158.8 (C), 157.8 (C), 142.2 (CH), 137.3 (C), 133.8 (C), 132.4 (CH), 130.2 (C), 128.3 (CH), 128.2 (CH), 127.2 (2 CH), 120.2 (CH), 116.2 (CH), 113.8 (2 CH), 111.4 (CH), 64.4 (CH2), 55.2 (2 CH3), 37.1 (CH), 30.7 (CH2), 21.1 (CH3), 19.1 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C25H30O4 394.2144, found 394.2147; IR (KBr): 2962, 1712, 1602, 1511, 1249, 7328 cm-1 (E)-Butyl 3-(4-methoxy-2-((E)-4-(3-methoxyphenyl)but-3-en-2-yl)phenyl)acrylate (3ga) S19

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 15.6 Hz, 1 H), 7.55 (d, J = 8.8 Hz, 1 H), 7.19 (t, J = 7.6 Hz, 1 H), 6.93 (d, J = 7.6 Hz, 1 H), 6.88 (s, 1 H), 6.84 (s, 1 H), 6.76 (td, J = 2.4 Hz, J = 8.8 Hz, 2 H), 6.04-6.29 (m, 2 H), 6.27 (d, J = 15.6 Hz, 1 H), 4.18 (t, J = 6.4 Hz, 2 H), 6.07-6.04 (m, 1 H), 3.80 (s, 3 H), 3.78 (s, 3 H), 1.73-1.64 (m, 2 H), 1.46-1.39 (m, 5 H), 0.95 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 167.2 (ester carbonyl), 161.2 (C), 159.7 (C), 146.6 (C), 141.4 (CH), 138.7 (C), 134.2 (CH), 129.3 (CH), 129.2 (CH), 128.3 (CH), 125.4 (C), 118.7 (CH), 117.6 (CH), 112.9 (CH), 112.8 (CH), 111.7 (CH), 111.3 (CH), 64.1 (CH2), 55.1 (CH3), 55.0 (CH3), 37.7 (CH), 30.7 (CH2), 20.7 (CH3), 19.1 (CH2), 13.6 (CH3); HRMS (EI+) calcd for C25H30O4 394.2144, found 394.2147; IR (KBr): 2962, 1704. 1604, 1488, 1164, and 570 cm-1 (E)-Butyl 3-(4-chloro-2-((E)-4-(3-chlorophenyl)but-3-en-2-yl)phenyl)acrylate (3ha)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.01 (d, J = 15.5 Hz, 1 H), 7.46 (d, J = 8.0 Hz, 1H), 7.31 (s, 1 H), 7.26 (s, 1H), 7.25-7.14 (m, 4 H), 6.32-6.28 (m, 3 H), 4.19 (t, J = 6.5 Hz, 2 H), 4.013.90 (m, 1 H), 1.69-1.63 (m, 2 H), 1.45-1.37 (m, 5 H), 0.94 (t, J = 7.5 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.7 (ester carbonyl), 145.9 (C), 140.8 (CH), 138.9 (C), 136.1 (C), 134.7 (CH), 134.4 (C), 131.5 (C), 129.7 (CH), 128.5 (CH), 128.3 (CH), 127.3 (CH), 127.2 (CH), 127.0 (CH), 126.1 (CH), 124.4 (CH), 120.8 (CH), 64.5 (CH2), 37.8 (CH), 30.7 (CH2), 20.6 (CH3), 19.1 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C23H24Cl2O2 402.1153, found 402.1146; IR (KBr): 2962, 1712, 1635, 1589, 1311, 1173 and 725 cm-1 (E)-Butyl 3-(3-((E)-4-(naphthalen-2-yl)but-3-en-2-yl)naphthalen-2-yl)acrylate (3ia)

S20

White solid; m.p. 125-127 °C; 1H NMR (400 MHz, CDCl3): δ 8.28 (d, J = 15.5 Hz, 1 H), 8.05 (s, 1 H), 7.83-7.73 (m, 6 H), 7.68 (s, 1 H), 7.57 (dd, J = 1.5 Hz, J = 8.0 Hz, 1 H), 7.49-7.38 (m, 4 H), 6.57 (d, J = 2.5 Hz, 2 H), 6.48 (d, J = 16.0 Hz, 1 H), 4.22 (t, J = 6.5 Hz, 2 H), 4.19-4.17 (m, 1 H), 1.73-1.66 (m, 2 H), 1.61 (d, J = 7.0 Hz, 3 H), 1.47-1.39 (m, 2 H), 0.95 (t, J = 7.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.9 (ester carbonyl), 142.9 (CH), 141.5 (C), 134.8 (C), 134.7 (CH), 134.1 (C), 133.6 (C), 132.7 (C), 132.4 (C), 131.8 (C), 129.6 (CH), 128.0 (CH), 127.9 (CH), 127.8 (CH), 127.5 (CH), 127.4 (CH), 126.9 (CH), 126.8 (CH), 126.1 (CH), 126.0 (CH), 125.8 (CH), 125.7 (CH), 125.6 (CH), 123.5 (CH), 120.7 (CH), 64.4 (CH2), 38.4 (CH), 30.7 (CH2), 20.9 (CH3), 19.2 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C31H30O2 434.2246, found 434.2245; IR (KBr): 2962, 1720, 1457, 1172 and 578 cm-1 (E)-Butyl 3-(2-cinnamylphenyl)acrylate (3ja) CO2n-Bu

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.08 (dd, J = 1.6 Hz, J = 16.4 Hz, 1 H), 7.61 (d, J = 7.6 Hz, 1 H), 7.37-7.19 (m, 8 H), 6.43-6.31 (m, 3 H), 4.23 (td, J = 2.0 Hz, J = 6.8 Hz, 2 H), 3.70 (d, J = 6.0 Hz, 2 H), 1.74-1.67 (m, 2 H), 1.48-1.42 (m, 2 H), 0.97 (td, J = 2.0 Hz, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.9 (ester carbonyl), 141.9 (CH), 139.3 (C), 137.2 (C), 133.4 (C), 131.4 (CH), 130.2 (CH), 130.1 (CH), 128.4 (2 CH), 128.3 (CH), 127.1 (CH), 126.8 (CH), 126.6 (CH), 126.1 (2 CH), 119.8 (CH), 64.3 (CH2), 36.5 (CH2), 30.7 (CH2), 19.1 (CH2), 13.6 (CH3); HRMS (EI+) calcd for C22H24O2 320.1776, found 320.1779; IR (KBr): 2695, 1712, 1635, 1481, 1450, 1271, 1172 and 671 cm-1 (E)-Butyl 3-(5-methyl-2-((E)-3-p-tolylallyl)phenyl)acrylate (3ka)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.01 (d, J = 15.6 Hz, 1 H), 7.40 (s, 1 H), 7.20-7.06 (m, 6 H), 6.37-6.21 (m, 3 H), 4.19 (t, J = 6.8 Hz, 2 H), 3.62 (d, J = 5.6 Hz, 2 H), 2.34 (s, 3 H), 1.79-1.63 (m, 2H), 1.47-1.38 (m, 2 H), 0.96 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 167.0 (ester carbonyl), 142.1 (CH), 136.8 (C), 136.6 (C), 136.3 (C), 134.5 (C), 133.2 (C), 131.1 (C), 131.0 (CH), 130.1 (CH), 129.1 (CH), 128.9 (CH), 127.6 (CH), 127.2 (CH), 126.0 (2 CH), 119.4 (CH), 64.3 (CH2), 36.1 (CH2), 30.7 (CH2), 21.1 (CH3), 20.9 (CH3), 19.2 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C24H28O2 348.2089, found 348.2084; IR (KBr): 2923, 2360, 1712, 1635, 1172 and 725 cm-1 (E)-Butyl 3-(2-cinnamyl-3-methylphenyl)acrylate (3la)

S21

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.11 (d, J = 15.6 Hz, 1 H), 7.48 (d, J = 7.2 Hz, 1 H), 7.32-7.18 (m, 7 H), 6.38 (d, J = 16.0 Hz, 1 H), 6.31-6.23 (m, 2 H), 4.23 (t, J = 6.8 Hz, 2 H), 3.70 (d, J = 5.2 Hz, 2 H), 2.40 (s, 3 H), 1.75-1.67 (m, 2 H), 1.50-1.41 (m, 2 H), 0.98 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.9 (ester carbonyl), 142.9 (CH), 137.4 (C), 137.2 (C), 137.1 (C), 134.0 (C), 131.9 (CH), 130.7 (CH), 128.3 (2 CH), 127.2 (CH), 127.0 (CH), 126.5 (CH), 126.0 (2 CH), 124.6 (CH), 120.1 (CH), 64.3 (CH2), 32.4 (CH2), 30.7 (CH2), 19.8 (CH3), 19.1 (CH2), 13.6 (CH3); HRMS (EI+) calcd for C23H26O2 334.1933, found 334.1921; IR (KBr): 2962, 1712, 1635, 1457, 1172 and 717 cm-1 (E)-Butyl 3-(2-cinnamyl-5-methylphenyl)acrylate (3ma)

O

O

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.04 (d, J = 15.6 Hz, 1 H), 7.43 (s, 1 H), 7.34 (d, J = 8.4 Hz, 2 H), 7.28 (t, J = 7.2 Hz, 2 H), 7.21-7.17 (m, 3 H), 4.21 (t, J = 6.4 Hz, 2 H), 3.65 (d, J = 5.6 Hz, 2 H), 2.36 (s, 3 H), 1.72-1.69 (m, 2 H), 1.67-1.41 (m, 2 H), 0.96 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 167.0 (ester carbonyl), 137.3 (C), 136.4 (C), 136.3 (C), 133.1 (C), 131.2 (CH), 131.0 (CH), 130.1 (CH), 128.6 (CH), 128.4 (2 CH), 127.1 (CH), 127.0 (CH), 126.1 (2 CH), 119.4 (CH), 64.3 (CH2), 36.1 (CH2), 30.7 (CH2), 20.9 (CH3), 19.1 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C23H26O2 334.1933, found 334.1928; IR (KBr): 2954, 1712, 1635, 1496, 1311, 786 and 771 cm-1 (E)-Butyl 3-(5-tert-butyl-2-cinnamylphenyl)acrylate (3na)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.10 (d, J = 16.0 Hz, 1 H), 7.62 (s, 1 H), 7.38 (dd, J = 2.0 Hz, J = 8.0 Hz, 1 H), 7.35 (d, J = 8.8 Hz, 2 H), 7.26 (t, J = 7.6 Hz, 2 H), 7.22 (t, J = 8.4 Hz, 2 H), 7.26 (t, J = 7.6 Hz, 2 H), 7.22 (t, J = 8.4 Hz, 2 H), 6.43-6.29 (m, 3 H), 4.22 (t, J = 7.2 Hz, 2 H), 3.66 (d, J S22

= 6.0 Hz, 2 H), 1.72-1.68 (m, 2 H), 1.46-1.31 (m, 2 H), 0.96 (t, J = 7.6 Hz, 3 H), 13C NMR (100 MHz, CDCl3): δ167.3 (ester carbonyl), 149.9 (C), 142.9 (CH), 137.6 (C), 136.8 (C), 133.1 (C), 131.5 (CH), 130.2 (CH), 128.8 (CH), 128.6 (2 CH), 127.7 (CH), 127.3 (CH), 126.4 (2 CH), 123.7 (CH), 119.6 (CH), 64.6 (CH2), 36.4 (CH2), 34.7 (C), 31.5 (3 CH3), 31.0 (CH2), 19.4 (CH2), 14.0 (CH3); HRMS (EI+) calcd for C26H32O2 376.2402, found 376.2400; IR (KBr): 2962, 1712, 1457, 1311, 1272,1172 and 725 cm-1 (E)-Butyl 3-(2-cinnamyl-5-fluorophenyl)acrylate (3oa)

O

O

F

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 7.96 (d, J = 16.0 Hz, 1 H), 7.32-7.01 (m, 7 H), 7.04 (t, J = 6.0 Hz, 1 H), 6.36-6.25 (m, 3 H), 4.20 (q, J = 8.0 Hz, 2 H), 3.64 (d, J = 5.6 Hz, 2 H), 1.691.61 (m, 2 H), 1.44-1.37 (m, 2 H), 0.97 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.6 (ester carbonyl), 162.8 (d, JC-F = 246.6 Hz, C), 140.8 (CH), 137.1 (C), 135.0 (C), 131.8 (d, JC-F = 7.6 Hz, C), 131.6 (C), 130.1 (C), 128.4 (2 CH), 128.1 (CH), 127.2 (CH), 126.1 (2 CH), 120.9 (CH), 117.9 (d, JC-F = 21.2 Hz, CH), 113.0 (d, JC-F = 21.9 Hz, CH), 64.5 (CH2), 35.8 (CH2), 30.6 (CH2), 19.1 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C22H23FO2 338.1682, found 338.1676; IR (KBr): 2954, 1712, 1172 and 840 cm-1 (E)-Butyl 3-(2-((E)-2-methyl-3-phenylallyl)phenyl)acrylate (3pa)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.07 (d, J = 15.6 Hz, 1 H), 7.59 (d, J = 7.2 Hz, 1 H), 7.34-7.17 (m, 8 H), 6.35 (dd, J = 1.2 Hz, J = 15.6 Hz, 1 H), 6.19 (s, 1 H), 4.19 (td, J = 0.8 Hz, J = 7.6 Hz, 2 H), 3.62 (s, 2 H), 1.83 (s, 3 H), 1.68-1.59 (m, 2 H), 1.44-1.39 (m, 2 H), 0.95 (t, J = 6.0 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.4 (ester carbonyl), 142.3 (CH), 138.9 (C), 138.1 (C), 137.3 (C), 134.1(C), 130.9 (CH), 129.9 (CH), 128.8 (2 CH), 127.9 (CH), 127.3 (CH), 127.0 (CH), 126.9 (CH), 126.6 (CH), 126.0 (CH), 119.5 (CH), 64.3 (CH2), 43.7 (CH2), 30.7 (CH2), 19.1 (CH2), 17.9 (CH3), 13.7 (CH3); HRMS (EI+) calcd for C23H26O2 334.1933, found 334.1939; IR (KBr): 2962, 2360, 1712, 1635, 1172, and 732 cm-1 2-Methyl 3-(2-(4-chloro-3-ethylhex-3-en-2-yl)phenyl)acrylate (3qc)

S23

Pale yellow oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.20 (d, J = 17.2 Hz, 1 H) 7.49 (d, J = 7.6 Hz, 1 H), 7.38-7.35 (m, 2 H), 7.27-7.24 (m, 1 H), 6.25 (d, J = 16.0 Hz, 1 H), 4.65-4.60 (m, 1 H), 3.79 (s, 3H), 2.44-2.28 (m, 2 H), 1.84-1.78 (m, 2 H), 1.42-1.39 (m, 6 H), 1.13-1.08 (m, 3 H), 0.517-0.42 (m, 3 H); 13C NMR (100 MHz, CDCl3): δ 167.1 (ester carbonyl), 143.1 (CH), 137.9 (C), 134.9 (C), 132.1(C), 129.8 (CH), 127.9 (C), 127.0 (CH), 126.8 (CH), 126.3 (CH), 119.5 (CH), 51.6 (CH3), 39.2 (CH), 28.6 (CH2), 23.5 (CH2), 21.7 (CH2), 17.1 (CH2), 12.8 (CH3), 12.6 (CH3), 12.4 (CH3); HRMS (EI+) calcd for C18H23ClO2 306.1387, found 306.1379; IR (KBr): 2969, 1720, 1635, 1457, 1311, 1272,1172 and 771 cm-1 (2E)-Butyl 3-(2-(hex-2-enyl)phenyl)acrylate (3ra)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.00 (d, J = 16.0 Hz, 1 H), 7.56 (d, J = 6.8 Hz, 1 H), 7.33-7.20 (m, 3 H), 6.34 (d, J = 16.0 Hz, 1 H), 5.56-5.38 (m, 2 H), 4.21 (td, J = 3.2 Hz, J = 6.8 Hz, 2 H), 2.46 (d, J = 5.6 Hz, 2 H), 1.99-1.94 (m, 2 H), 1.72-1.65 (m, 2 H), 1.47-1.25 (m, 4 H), 0.98 (t, J = 7.2 Hz, 3 H), 0.85 (t, J = 5.6 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 167.2 (ester carbonyl), 142.3 (CH), 140.2 (C), 133.3 (C), 132.3 (CH), 130.0 (2 CH), 128.1 (CH), 126.5 (2 CH), 119.4 (CH), 64.3 (CH2), 36.4 (CH2), 34.5 (CH2), 30.7 (CH2), 22.4 (CH2), 19.2 (CH2), 13.7 (CH3), 13.5 (CH3); HRMS (EI+) calcd for C19H26O2 286.1933, found 286.1941; IR (KBr): 2962, 1712, 1635, 1311, 1172, 971 and 725 cm-1

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.06 (d, J = 16.0 Hz, 1 H), 7.35 (d, J = 7.2 Hz, 1 H), 7.28 (td, J = 2.0 Hz, J = 9.2 Hz, 2 H), 7.20 (t, J = 6.8 Hz, 1 H), 6.41-6.30 (m, 3 H), 4.21 (t, J = 7.2 Hz, 2 H), 3.69 (d, J = 6. 0 Hz, 2 H), 1.71-1.62 (m, 2 H), 1.46-1.41 (m, 2 H), 0.96 (t, J = 7.6 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.9 (ester carbonyl), 141.9 (CH), 139.2 (C), 137.2 (C), 133.3 (C), 131.5 (CH), 128.4 (2 CH), 128.3 (CH), 127.1 (CH), 126.1 (2 CH), 119.8 (CH), 64.3 (CH2), 36.5 (CH2), 30.7 S24

(CH2), 19.1 (CH2), 13.7 (CH3); HRMS (EI+) calcd for C22H20D4O2 324.2027, found 324.2020; IR (KBr): 2962, 1712, 1635, 1303, 1180, 979 and 570 cm-1 (E)-3-(2-Cinnamylphenyl)-N,N-dimethylacrylamide (3jk)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.01 (d, J = 15.6 Hz, 1 H), 7.56 (d, J = 8.0 Hz, 1 H), 7.34-7.20 (m, 7 H), 7.18 (t, J = 5.6 Hz, 1 H), 6.78 (d, J = 15.6 Hz, 1 H), 6.40-6.30 (m, 2 H), 3.68 (d, J = 5.2 Hz, 2 H), 3.13 (s, 3 H), 3.06 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ 166.7 (amide carbonyl), 140.0 (CH), 139.2 (C), 137.2 (C), 134.4 (C), 131.3 (CH), 130.1 (CH), 129.4 (CH), 128.4 (CH), 128.3 (2 CH), 127.0 (CH), 126.6 (CH) 126.5 (CH), 126.0 (2 CH), 119.3 (CH), 37.3 (CH3), 36.4 (CH2), 35.8 (CH3); HRMS (EI+) calcd for C20H21NO 291.1623, found 291.1623; IR (KBr): 3069, 2930, 1637, 1617, 1485, 1387, 717 and 647cm-1 (E)-3-(2-Cinnamylphenyl)acrylonitrile (3jm)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 7.75 (d, J = 16.4 Hz, 1 H), 7.50 (d, J = 8.0 Hz, 1H), 7.40-7.21 (m, 7 H), 6.31-6.29 (m, 2 H), 5.82 (dd, J = 1.2 Hz, J = 16.4 Hz, 1 H), 3.63 (d, J = 4.4 Hz, 2 H); 13C NMR (100 MHz, CDCl3): δ 148.2 (CH), 139.0 (C), 136.9 (C), 132.6 (C), 131.8 (CH), 131.1 (CH), 130.6 (CH), 128.5 (2 CH), 127.7 (CH), 127.4 (CH), 127.2 (CH), 126.1 (2 CH), 125.9 (CH), 118.2 (C), 97.7 (CH), 36.4 (CH2); HRMS (EI+) calcd for C18H15N 245.1204, found 245.1202; IR (KBr): 3069, 2969, 2923, 2228, 1617, 1483, 1434, 1278 and 809 cm-1 1-Cinnamyl-2-((E)-2-(phenylsulfonyl)vinyl)benzene (3jn)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.06 (d, J = 15.2 Hz, 1 H), 7.76 (d, J = 8.4 Hz, 2 H), 7.49 (t, J = 6.0 Hz, 2 H), 7.48 (t, J = 4.4 Hz, 1 H), 7.39-7.22 (m, 9 H), 6.78 (d, J = 15.2 Hz, 1 H), 6.41-6.26 (m, 2 H), 3.72 (d, J = 6.0 Hz, 2 H); 13C NMR (100 MHz, CDCl3): δ 140.4 (C), 140.0 (CH), 139.9 (C), 136.9 (C), 133.1 (CH), 131.5 (CH), 131.3 (C), 131.1 (CH), 130.6 (CH), 129.1 (2 CH), 128.4 (2 S25

CH), 128.2 (2 CH), 127.5 (2 CH), 127.2 (CH), 127.1 (CH), 127.0 (CH), 126.1 (2 CH), 36.9 (CH2); HRMS (EI+) calcd for C23H20O2S 360.1184, found 360.1181; IR (KBr): 3031, 2969, 1604, 1454, 1312, 1142, 860 and 532 cm-1 (2E)-Butyl 3-(2-(hex-2-enyl)phenyl)acrylate ([d4]-3ra)

Colourless oily liquid; 1H NMR (400 MHz, CDCl3): δ 8.01 (d, J = 16.0 Hz, 1 H), 6.34 (d, J = 15.6 Hz, 1 H), 5.53-5.39 (m, 2 H), 3.78 (s, 3 H), 3.45 (dd, J = 1.2 Hz, J = 6.0 Hz, 2 H), 1.98-1.92 (m, 2 H), 1.37-1.26 (m, 2 H), 0.81 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3): δ 167.4 (ester carbonyl), 142.6 (CH), 140.2 (C), 133.1 (C), 132.4 (CH), 128.0 (CH), 118.9 (CH), 51.6 (CH3), 36.3 (CH2), 34.5 (CH2), 22.4 (CH2), 13.5 (CH3); HRMS (EI+) calcd for C16H16D4O2 248.1714, found 248.1711.

References: 1. D. D. Perrin, W. L. F Armarego. In Purification of Laboratory Chemicals, 3rd ed.; Pergamon Press: New York, 1988. 2. C.-C. Wang, P.-S. Lin, C.-H. Cheng, Tetrahedron Lett. 2004, 45, 6203. 3. H. Tsukamoto, T. Uchiyama, T. Suzuki, Y. Kondo, Org. Biomol. Chem., 2008, 6, 3005. 4. T. Tsuchimoto, K. Tobita, T. Hiyama, S.-I. Fukuzawa, J. Org. Chem. 1997, 62, 6997. 5. S. Biswas, S. Maiti, U. Jana, Eur. J. Org. Chem. 2009, 14, 2354

S26

NOE Data of Compound 3g

5.70

0.64

0.37 CO2H H H3C H

H

5.55

S27

1

H and 13C NMR spectra of compound 3a.

S28

1

H and 13C NMR spectra of compound 3b.

S29

1

H and 13C NMR spectra of compound 3c.

S30

1

H and 13C NMR spectra of compound 3d.

S31

1

H and 13C NMR spectra of compound 3e.

S32

1

H and 13C NMR spectra of compound 3f.

S33

1

H and 13C NMR spectra of compound 3g.

S34

1

H and 13C NMR spectra of compound 3h.

S35

1

H and 13C NMR spectra of compound 3i.

.

S36

1

H and 13C NMR spectra of compound 3j.

S37

1

H and 13C NMR spectra of compound 3k.

S38

1

H and 13C NMR spectra of compound 3l.

S39

1

H and 13C NMR spectra of compound 3m.

S40

1

H and 13C NMR spectra of compound 3n.

S41

1

H and 13C NMR spectra of compound 3ba.

S42

1

H and 13C NMR spectra of compound 3ca.

S43

1

H and 13C NMR spectra of compound 3da.

S44

1

H and 13C NMR spectra of compound 3ea.

S45

1

H and 13C NMR spectra of compound 3fa.

S46

1

H and 13C NMR spectra of compound 3ga.

S47

1

H and 13C NMR spectra of compound 3ha.

S48

1

H and 13C NMR spectra of compound 3ia.

S49

1

H and 13C NMR spectra of compound 3ja

S50

1

H and 13C NMR spectra of compound 3ka

S51

1

H and 13C NMR spectra of compound 3la.

S52

1

H and 13C NMR spectra of compound 3ma.

S53

1

H and 13C NMR spectra of compound 3na.

S54

1

H and 13C NMR spectra of compound 3oa.

S55

1

H and 13C NMR spectra of compound 3oa.

S56

1

H and 13C NMR spectra of compound 3qa.

S57

1

H and 13C NMR spectra of compound 3ra.

S58

1

H and 13C NMR spectra of compound [d5]-1ja.

S59

1

H and 13C NMR spectra of compound 3jk.

S60

1

H and 13C NMR spectra of compound 3jm.

S61

1

H and 13C NMR spectra of compound 3jn

S62

1

H and 13C NMR spectra of compound 2-D bromobenzene.

S63

1

H and 13C NMR spectra of compound [d5]-1r.

S64

1

H and 13C NMR spectra of compound [d4]-3rc.

S65

1

H and 13C NMR spectra of compound [d1]-1j.

S66

1

H and 13C NMR spectra of compound [d1]-3ja + 3ja.

S67

S68

ORTEP Diagram of Compound 3l

S69

Table 1. Crystal data and structure refinement for 110642LT_0M (3l). Identification code

110642lt_0m

Empirical formula

C52 H50 N2 O2

Formula weight

734.94

Temperature

100(2) K

Wavelength

0.71073 Å

Crystal system

Triclinic

Space group

P -1

Unit cell dimensions

a = 8(2) Å

α= 80.57°.

b = 12.648 Å

β= 80.56°.

c = 19.339 Å

γ = 89.89°.

Volume

2013(476) Å3

Z

2

Density (calculated)

1.212 Mg/m3

Absorption coefficient

0.073 mm-1

F(000)

784

Crystal size

0.25 x 0.22 x 0.12 mm3

Theta range for data collection

1.08 to 26.40°.

Index ranges

-10

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