Carbonylative Coupling of Allylic Acetates with

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Carbonylative Coupling of Allylic Acetates with. Arylboronic Acids. Wei Ma, a. Ting Yu, Dong Xue,* a. Chao Wang a and Jianliang Xiao* a,b a. Key Laboratory of ...

Electronic Supplementary Material (ESI) for ChemComm. This journal is © The Royal Society of Chemistry 2015

Carbonylative Coupling of Allylic Acetates with Arylboronic Acids Wei Ma,a Ting Yu, Dong Xue,*a Chao Wanga and Jianliang Xiao*a,b a

Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of

Education and School of Chemistry and Chemical

Engineering, Shaanxi Normal University, Xi’an, 710062, China b

Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK

Contents 1. General information

S2

2. Optimization of reaction conditions

S2

3. Typical procedure for allylic carbonylation of aryl boronic acids with allyl acetate

S5

4. Typical reaction procedure for the synthesis of α, β-unsaturated ketones

S6

5. Procedures for study of reaction mechanism.

S7

6. Data for products

S8

7. References

S17

8. Copies of the 1H NMR and 13C NMR spectra of products

S19

S1

1. General information NMR spectra were recorded on a 400 MHz spectrometer with TMS as the internal standard. All coupling constants (J values) were reported in Hertz (Hz). Data are presented as follows: chemical shift in ppm and multiplicity as s = singlet, d = doublet, t = triplet, q = quartet and m = multiplet. Thin layer chromatography (TLC) was performed on glass backed silica gel plates. Column chromatography was performed on silica gel 200-300 mesh. Flash chromatography was performed with freshly distilled solvents. HRMS (ESI) were performed on a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer.

2. Optimization of reaction conditions 2.1 The purification of aryl boronic acids Aryl boronic acids were purified by the following method: 10 mmol of arylboronic acid was dissolved in 15 mL of 1 M NaOH solution and stirred for 20 min. 1 M HCl solution was added dropwise and a white precipitate formed instantly when pH value was adjusted to 7. The white solid was filtered and recrystallised from H2O/CH3CN. The solid was filtered, dried under reduced pressure and used directly. 2.2 Typical reaction procedure for the optimization of reaction conditions The reaction was carried out in an autoclave containing a 10 mL Teflon reaction tube. Pd source (0.02 mmol), ligand (0.05 mmol) and a magnetic stir bar were placed in the tube, which was then capped with a stopper. Then, aryl boronic (0.5 mmol), allyl acetate (1mmol), solvent (3 mL) were added to the tube. The tube was placed in the autoclave. Once sealed, the autoclave was purged several times with CO at room temperature and heated in an oil bath at 120 °C for 12 hours. The autoclave was then cooled to room temperature and vented to discharge the excess CO. Water (10 mL) was added, and the product was extracted with EA (3×3 mL). The organic layers were washed with brine, dried over Na2SO4, and evaporated. The crude product was purified by column chromatography on silica gel using a mixture of ethyl acetate and petroleum ether as eluent to give the desired product. Structures of ligands screened in S2

this paper are shown in Scheme S1. Table S1 Screening of ligands and Pd sources

Entry

cat

ligand

Base

solvent

Yield

1

Pd(PPh3)4

0

KOH

PhCH3

7.5%

2

Pd(PPh3)4

0

0

PhCH3

trace

0

KOH

PhCH3

0

0

KOH

PhCH3

0

0

KOH

PhCH3

0

PPh3 (2%)

KOH

PhCH3

10%

PPh3 (8%)

KOH

PhCH3

0

PPh3 (8%)

KOH

PhCH3

15%

3 4 5 6 7 8

No Pd(OAc)2 Pd(dba)3 Pd(PPh3)4 Pd(OTFA)2 Pd(OAc)2

9

PdCl2

PPh3 (8%)

KOH

PhCH3

0

10

Pd(OAc)2

[HP(t-Bu)3]BF4

KOH

PhCH3

9%

11

Pd(OAc)2

DPPF

KOH

PhCH3

trace

12

Pd(OAc)2

DPPE

KOH

PhCH3

0

13

Pd(OAc)2

DPPP

KOH

PhCH3

0

14

Pd(OAc)2

BINAP

KOH

PhCH3

0

15

Pd(OAc)2

A

KOH

PhCH3

0

16

Pd(OAc)2

B

KOH

PhCH3

0

17

Pd(OAc)2

C

KOH

PhCH3

16%

18

Pd(OAc)2

PCy3

KOH

PhCH3

30%

S3

Scheme S1 Structures of ligands.

Table S2 Screening of base and additive

Entry

cat

ligand

Base

solvent

1

Pd(OAc)2

PCy3

KF·2H2O

PhCH3

23%

2

Pd(OAc)2

PCy3

NaHCO3

PhCH3

0

3

Pd(OAc)2

PCy3

NEt3

PhCH3

trace

4

Pd(OAc)2

PCy3

HCOONa·2H2O

PhCH3

trace

5

Pd(OAc)2

PCy3

NaOH

PhCH3

35%

6

Pd(OAc)2

PCy3

NaOH

PhCH3

7

Pd(OAc)2

PCy3

K3PO4

PhCH3

30%

8

Pd(OAc)2

PCy3

K3PO4·3H2O

PhCH3

60%

9

Pd(OAc)2

PCy3

K3PO4·3H2O

PhCH3

H2O (2eq)

64 %

10

Pd(OAc)2

PCy3

K3PO4·3H2O

PhCH3

H2O (4eq)

72%

11

Pd(OAc)2

PCy3

K3PO4·3H2O

PhCH3 / dioxane

H2O (2eq)

81%

S4

additive

H2O (2eq)

Yield

70%

Scheme S2 Effect of water

In the case of aryl boroxine (0.17 mmol), a dramatically decreased yield (29%) of 3a was observed. Therefore, water was added to reduce aryl boroxiane produced. The yield of 3a increased to 70% (Sheme S2, eq 4), when p-tolylboronic acid (0.5 mmol) was used as substrate and 2 equiv of water as additive. General reaction conditions for Scheme S2: Allylic acetoxy (1mol, 2eq), Pd(OAc)2 (4% mol), PCy3 (10% mol), NaOH (0.5 mmol), toluene (3 mL), under 5 bar of CO. The reaction was stirred at 120 o

C for 12 h. The yield of 3a was detected by NMR.

3. Typical procedure for allylic carbonylation of aryl boronic acids with allyl acetate The reaction was carried out in an autoclave containing a 10 mL Teflon reaction tube. Pd(OAc)2 (4% mol), PCy3 (10% mol), and a magnetic stir bar were placed in the tube, which was then capped with a stopper. Then, aryl boronic acid (0.5 mmol), allyl acetate (1.0 mmol), solvent (toluene/dioxane = 1 : 1, 3 mL), K3PO4·3H2O (0.5 mmol) S5

and H2O (18mg, 2 eq) were added to the tube. The tube was placed in the autoclave. Once sealed, the autoclave was purged several times and then pressurized to 5 atm with CO at room temperature and heated in an oil bath at 120 °C for 12 hours (for substrates 1a, 1b, 1c, 1d, 1e, 1f, 1i, 1k, 1l, 1o, 1p) or 24 hours (for substrates 1g, 1h, 1j, 1m, 1n). The autoclave was then cooled to room temperature and vented to discharge the excess CO. Water (10 mL) was added, and the product was extracted with EA (3×3 mL). The organic layers were washed with brine, dried over Na2SO4, and evaporated. The crude product was purified by column chromatography on silica gel using a mixture of ethyl acetate and petroleum ether as eluent to give α, β-unsaturated aryl ketones.

4. Typical procedure for carbonylation of allyl acetates with p-tolylboronic acid Method A: The reaction was carried out in an autoclave containing a 10 mL Teflon reaction tube. Pd(OAc)2 (4% mol), PCy3 (10% mol), and a magnetic stir bar were placed in the tube, which was then capped with a stopper. Then, aryl boronic acid (0.5 mmol), allyl acetate (1.0 mmol), solvent (toluene, 3 mL) and K3PO4 (0.5 mmol) were added to the tube. The tube was placed in the autoclave. Once sealed, the autoclave was purged several times and then pressurized to 5 atm with CO at room temperature and heated in an oil bath at 120 °C for 24 hours. The autoclave was then cooled to room temperature and vented to discharge the excess CO. Water (10 mL) was added, and the product was extracted with EA (3×3 mL). The organic layers were washed with brine, dried over Na2SO4, and evaporated. The crude product was purified by column chromatography on silica gel using a mixture of ethyl acetate and petroleum ether as eluent to give the desired products 4b-e.

Method B: The reaction was carried out in an autoclave containing a 10 mL Teflon reaction tube. Pd(OAc)2 (4% mol), PCy3 (10% mol), and a magnetic stir bar were placed in the tube, which was then capped with a stopper. Then, aryl boronic acid (0.5 mmol), allyl acetate (1.0 mmol), solvent (toluene / dioxane = 1:1, 3 mL), K3PO4·3H2O (0.5 mol) and H2O (18 mg, 2 eq) were added to the tube. The tube was then placed in the autoclave. Once sealed, the autoclave was purged several times and S6

then pressurized to 5 atm with CO at room temperature and heated in an oil bath at 120 °C for 24 hours (for substrates 2f, 2g, 2h, 2l, 2m, 2n) or 12 hours (for substrates 2i, 2j, 2k). The autoclave was then cooled to room temperature and vented to discharge the excess CO. Water (10 mL) was added, and the product was extracted with EA (3×3 mL). The organic layers were washed with brine, dried over Na2SO4, and evaporated. The crude product was purified by column chromatography on silica gel using a mixture of ethyl acetate and petroleum ether as eluent to give the desired products.

5. Procedures for study of reaction mechanism An autoclave containing a 10 mL Teflon reaction tube was charged with a magnetic stir bar. p-Tolylboronic acid (68 mg, 0.5 mmol, 1eq), 2f (114 mg, 2eq), Pd(OAc)2 (4 mg, 4% mol), PCy3 (14 mg, 10% mol), K3PO4·3H2O (133 mg, 1 eq), toluene / dioxane = (1 : 1) (3 mL) and water (18 mg, 2 eq.) were added to the tube with a syringe. The tube was placed in the autoclave. Once sealed, the autoclave was pressurized with CO (5 bar) and heated in an oil bath at 120 °C for 1 h or 24 h. The yields of 4f and 4f-a were determined by NMR. 6. Data for products 3a. (E)-1-(p-tolyl)but-2-en-1-one:

Yield: 81% (12 h, 65 mg); pale yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.83 (d, J = 8.1 Hz, 2 H), 7.24 (d, J = 2.8 Hz, 2 H), 7.09 – 7.00 (m, 1H), 6.9 (d, J = 15.3 Hz, 1 H), 2.40 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 190.2, 144.4, 143.3, 135.3, 129.2, 128.6, 127.5, 21.6, 18.5; IR (KBr): 3082, 1671, 1621, 1443, 966, 799, 742 cm-1; HRMS (ESI) Calcd for C11H12O [M] + Na+ = 183.0782, Found = 183.0775. 3b. (E)-1-phenylbut-2-en-1-one:

S7

Yield: 71% (52 mg); pale yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.92 (d, J = 7.8 Hz, 2 H), 7.54 (t, J = 6.6 Hz, 1 H), 7.46 (t, J = 7.5 Hz, 2 H), 7.11–7.01 (m, 1 H), 6.91 (d, J = 15.3 Hz, 1 H), 2.00 (d, J = 6.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 190.8 145.0, 137.9, 132.6, 128.5, 127.6, 18.6; IR (KBr): 3059, 1671, 1624, 1443, 966, 691 cm-1; HRMS (ESI) Calcd for C10H10O [M] + Na+ = 169.0629, Found = 169.0666. 3c. (E)-1-(4-ethylphenyl)but-2-en-1-one:

Yield: 73% (63.5 mg); pale yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.87 (d, J = 8.3 Hz, 2 H), 7.28 (d, J = 8.3 Hz, 2 H), 7.11-7.02 (m, 1 H), 6.91 (dd, J = 15.3 Hz, J = 1.5 Hz, 1 H), 2.70 (dd, J = 15.2 Hz, J = 7.6 Hz, 2 H), 1.99 (dd, J = 6.8 Hz, J = 1.5 Hz, 3H);

13

C NMR (100 MHz, CDCl3) δ (ppm): 190.3, 149.6, 144.4, 135.6, 128.7,

128.0, 127.5, 28.9, 18.5, 15.1. IR (KBr): 3031, 1671, 1607, 1413, 969, 810 cm-1; HRMS (ESI) Calcd for C12H14O [M] + Na+ = 197.0942, Found = 197.0940. 3d. (E)-1-(4-propylphenyl)but-2-en-1-one:

Yield: 71% (66 mg); pale yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.86 (d, J = 8.2 Hz, 2 H), 7.26 (d, J = 8.1 Hz, 2 H), 7.11-7.02 (m, 1 H), 6.91 (dd, J = 15.3 Hz, J = 1.4 Hz, 1 H), 2.64 (t, J = 7.5 Hz, 2 H), 1.98 (dd, J = 6.8 Hz, J = 1.3Hz, 3H), 1.66 (m, 2 H), 0.94 (t, J = 7.3 Hz, 3H);

13

C NMR (100 MHz, CDCl3) δ (ppm): 190.3, 148.0,

144.4, 135.6, 128.7, 128.6, 127.5 38.0, 24.2, 18.5, 13.7. IR (KBr): 3036, 1668, 1618, 1440, 1299, 969 cm-1; HRMS (ESI) Calcd for C13H16O [M] + Na+ = 211.1094, Found = 211.1087. 3e. (E)-1-(4-(tert-butyl)phenyl)but-2-en-1-one:

Yield: 85% (86 mg); pale yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm) 7.88 (d, J = 8.2 Hz, 2 H), 7.48 (d, J = 8.2 Hz, 2 H), 7.11-7.02 (m, 1 H), 6.91 (d, J = 15.3 Hz, 1 S8

H), 1.99 (d, J = 6.8 Hz, 3H), 1.34 (s, 9 H);

13

C NMR (100 MHz, CDCl3) δ (ppm):

190.3, 156.3, 144.5, 135.3, 128.5, 127.5, 125.5, 35.1, 31.1, 18.6; IR (KBr): 3042, 1671, 1621, 1440, 966, 810 cm-1; HRMS (ESI) Calcd for C14H18O [M]+Na+ = 225.1251, Found = 225.1240.

3f. (E)-1-([1, 1’-biphenyl]-4-yl)but-2-en-1-one:

Yield: 60% (67 mg); white solid, Mp (91-92 °C). 1H NMR (400 MHz, CDCl3) δ (ppm): 8.01 (d, J = 8.4 Hz, 2 H), 7.68 (d, J = 8.4 Hz, 2 H), 7.62 (d, J = 7.2 Hz, 2 H), 7.48-7.37 (m, 3 H), 7.15 – 7.06 (m, 1H), 6.95 (dd, J = 15.2 Hz, J = 1.5 Hz, 1 H), 2.01 (dd, J = 6.8 Hz, J = 1.5 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm): 190.2, 145.3, 144.9, 140.0, 136.6, 129.1, 128.9, 127.5, 127.3, 127.2, 18.6; IR (KBr): 3056, 1665, 1618, 1440, 919, 760 cm-1; HRMS (ESI) Calcd for C16H14O [M] + Na+ = 245.0937, Found = 245.0931.

3g. (E)-1-(4-methoxyphenyl)but-2-en-1-one:

Yield: 62% (54 mg); colorless oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.93 (d, J = 8.8 Hz, 2 H), 7.09 – 7.00 (m, 1 H), 6.94-6.89 (m, 3 H), 3.85 (s, 3 H), 1.97 (dd, J = 6.7 Hz, J = 1.2 Hz, 3 H);

13

C NMR(100 MHz, CDCl3) δ (ppm): 188.9, 163.3, 143.9,

130.8, 127.2, 113.7, 55.4, 18.5; IR (KBr): 3067, 1665, 1612, 1443, 1027, 1071, 813 cm-1; HRMS (ESI) Calcd for C11H12O2 [M] + Na = 199.0730, Found = 199.0725. 3h. (E)-1-(4-chlorophenyl)but-2-en-1-one:

S9

Yield: 30% (27 mg); colorless oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.87 (d, J = 8.6 Hz, 2 H), 7.44 (d, J = 8.6 Hz, 2H), 7.13 – 7.04 (m, 1H), 6.87 (dd, J = 15.3 Hz, J = 1.6 Hz, 1 H), 2.01(dd, J = 6.9 Hz, J = 1.6 Hz, 3 H);

13

C NMR (100 MHz, CDCl3) δ

(ppm): 189.4, 145.6, 139.0, 136.2, 129.9, 128.8, 127.1, 18.6; IR (KBr): 3061, 1668, 1618, 1260, 1091, 805 cm-1; HRMS (ESI) Calcd for C10H9ClO [M] + Na+ = 203.0234, Found = 203.0218.

3i. (E)-1-(m-tolyl)but-2-en-1-one:

Yield: 88% (70 mg); colorless oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.74–7.70 (m, 2 H), 7.37-7.32 (m, 2 H), 7.11-7.02 (m, 1 H), 6.90 (dd, J = 15.3 Hz, J = 1.5 Hz, 1 H), 2.41 (s, 3 H), 2.00 (dd, J = 6.8 Hz, J = 1.5 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 190.9, 144.7, 138.3, 137.9, 133.3, 129.0, 128.3, 127.7, 125.7, 21.3, 18.5; IR (KBr): 2959, 1651, 1615, 1257, 1099, 802 cm-1; HRMS (ESI) Calcd for C11H12O [M] + Na+ = 183.0780, Found=183.0776.

3j. (E)-1-(3-methoxyphenyl)but-2-en-1-one:

Yield: 78% (69mg); pale yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.50 – 7.46 (m, 2 H), 7.36 (t, J = 8.0 Hz, 2 H), 7.12-7.03 (m, 2 H), 7.12-7.03 (m, 2H), 6.89 (dd, J = 15.3 Hz, J = 1.5 Hz, 1 H), 3.86 (s, 3 H), 2.00 (dd, J = 6.8 Hz, J = 1.5 Hz, 3 H); 13

C NMR (100 MHz, CDCl3) δ (ppm): 190.5, 159.8, 145.1, 139.3, 129.5, 127.6, 121.7,

119.2, 112.8, 55.4, 18.6; IR (KBr): 3003, 1671, 1624, 1460, 1035, 780 cm-1; HRMS (ESI) Calcd for C11H12O2 [M] + Na+ = 199.0730, Found = 199.0721. 3k. (E)-1-(3,5-dimethylphenyl)but-2-en-1-one:

S10

Yield: 86% (75 mg); pale yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.35 (s, 2 H), 7.17 (s, 1 H), 7.09-7.00 (m, 1 H), 6.90 (dd, J = 15.3 Hz, J = 1.5 Hz, 1 H), 2.36 (s, 6 H), 1.98 (dd, J = 6.8 Hz, J = 1.6 Hz, 3H);

13

C NMR (100 MHz, CDCl3) δ (ppm):

191.1, 144.5, 138.1, 138.0, 134.2, 127.8, 129.4, 126.3, 21.2, 18.5; IR (KBr): 3042, 1674, 1601, 1307, 1188, 1043 cm-1; HRMS (ESI) Calcd for C12H14O [M] + Na+ = 197.0938, Found = 197.0931.

3l. (E)-1-(o-tolyl)but-2-en-1-one:

Yield: 63% (50 mg); colorless oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.37-7.30 (m, 2 H), 7.26-7.20 (m, 2 H), 6.77- 6.68 (m, 1 H), 6.50 (d, J = 15.7 Hz, 1 H), 2.38(s, 3 H), 1.94 (d, J = 6.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 196.9, 146.7, 139.0, 136.6, 132.4, 131.1, 130.1, 127.9, 125.2, 20.0, 18.5; IR (KBr): 3021, 1651, 1621, 1451, 1032, 763 cm-1. HRMS (ESI) Calcd for C11H12O [M] + Na+ = 183.0780, Found = 183.0776.

3m. (E)-1-(2-fluorophenyl)but-2-en-1-one:

Yield: 60% (49 mg); pale yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.69 (td, J = 7.5Hz, J = 1.8 Hz, 1H), 7.51-7.45 (m, 1 H) ,7.22 (td, J = 7.6 Hz, J = 1.0 Hz 1 H), 7.14 – 7.09 (m, 1 H), 7.04-6.95 (m, 1 H), 6.77-6.71 (m, 1 H), 1.98 (dd, J = 6.9 Hz, J = 1.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm): 188.6 (d, JC-F = 2.2 Hz), 159.9 (d, JC-F = 251 Hz), 144.7, 132.5 (d, JC-F = 8.6 Hz), 130.1 (d, JC-F = 5.4 Hz), 129.7 (d, JC-F = 2.8 Hz), 126.0 (d, JC-F = 13.8 Hz), 123.3 (d, JC-F = 3.5 Hz), 115.4 (d, JC-F = 22.8 Hz),

S11

17.5; IR (KBr): 3006, 1674, 1649, 1454, 1035, 777 cm-1. HRMS (ESI) Calcd for C10H9FO [M] + Na+ = 187.0530, Found = 187.0524.

3n. (E)-1-(2-chlorophenyl)but-2-en-1-one:

Yield: 68% (61 mg); colorless oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.42-7.29 (m, 4 H), 6.76-6.67 (m, 1 H), 6.48 (dd, J = 15.7 Hz, J = 1.6 Hz, 1 H), 1.96 (dd, J = 6.8 Hz, J = 1.6 Hz, 3H);

13

C NMR (100 MHz, CDCl3) δ (ppm): 194.2, 148.0, 139.0, 132.0,

131.1, 130.1, 129.0, 126.6, 18.6; IR (KBr): 3059, 1660, 1618, 1435, 1038, 763 cm-1; HRMS (ESI) Calcd for C10H9ClO [M] + Na+ = 203.0234, Found = 203.0231.

3o. (E)-1-(thiophen-3-yl)but-2-en-1-one:

Yield: 66% (50 mg); pale yellow oil. 1H NMR (400 MHz, CDCl3) δ (ppm): 7.75 (d, J = 3.4 Hz, 1 H), 7.63 (d, J = 4.8 Hz, 1 H), 7.17-7.08 (m, 2 H), 6.82 (d, J = 15.2 Hz, 1 H), 1.98 (d, J = 6.9 Hz, 3H);

13

C NMR (100 MHz, CDCl3) δ (ppm): 182.2, 145.1,

144.2, 133.6, 131.8, 128.1, 126.9, 18.4. IR (KBr): 3097, 1665, 1618, 1415, 1293, 1027 cm-1. HRMS (ESI) Calcd for C8H8OS [M] + Na+ = 175.0184, Found = 175.0182.

3p. (E)-1-(naphthalen-1-yl)but-2-en-1-one:

Yield: 80% (78 mg); pale yellow oil. 1H NMR (400M Hz, CDCl3) δ (ppm): 8.25 (d, J = 7.8 Hz, 1 H), 7.95 (d, J = 8.2 Hz, 1 H), 7.88 (d, J = 7.4 Hz, 1 H), 7.65 (d, J = 7.0 Hz, 1 H), 7.57-7.47 (m, 3 H), 6.90-6.81 (m, 1 H), 6.68 (d, J = 15.6 Hz, 1 H), 1.97 (d, J = S12

6.8 Hz, 3 H), 7.03 (dd, J = 1.4 Hz, J = 5.2 Hz, 1 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 196.1, 146.9, 136.9, 133.8, 132.8, 131.3, 130.5, 128.3, 127.3, 126.9, 126.4, 125.6, 124.4, 18.6; IR (KBr): 3056, 1668, 1621, 1296, 1185, 816 cm-1; HRMS (ESI) Calcd for C14H12O [M] + Na+ = 219.0782, Found = 219.0772.

4b. (E)-4-phenyl-1-(p-tolyl)but-2-en-1-one

Yield: 55% (65 mg); pale yellow oil. 1H NMR (400M Hz, CDCl3) δ (ppm): 7.90 (d, J = 8.2 Hz, 2 H), 7.37 (d, J = 7.3 Hz, 2 H), 7.31-7.19 (m, 5 H), 6.56-6.43 (m, 2 H), 3.87 (d, J = 6.1 Hz, 3 H), 2.4 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 197.6, 144.0, 137.1, 134.2, 133.4, 129.4, 128.5, 128.4, 127.4, 126.3, 122.8, 42.7, 21.7; IR (KBr): 3028, 1674, 1604, 1257, 1177, 694 cm-1; HRMS (ESI) Calcd for C17H16O [M] + Na+ = 259.1099, Found = 259.1096.

4c. (E)-4-(m-tolyl)-1-(p-tolyl)but-2-en-1-one

Yield: 56% (70 mg); pale yellow oil; 1H NMR (400M Hz, CDCl3) δ (ppm): 7.91 (d, J = 8.1 Hz, 2 H), 7.28 (d, J = 8.0 Hz, 2 H), 7.21-7.18 (m, 3 H), 7.04 (d, J = 5.7 Hz, 1 H), 6.54 – 6.43 (m, 2 H), 3.88 (d, J = 5.9 Hz, 2 H), 2.42 (s, 3 H), 2.34 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 197.7, 144.0, 141.3, 138.0, 137.0, 134.2, 133.5, 129.4, 128.5, 128.4, 128.2, 126.9, 123.5, 122.6, 42.7, 21.7, 21.4; IR (KBr): 3028, 1674, 1607, 1282, 1179, 752 cm-1; HRMS (ESI) Calcd for C18H18O [M] + H+ = 251.1430, Found = 251.1424.

4d. (E)-4-(2-ethylphenyl)-1-(p-tolyl)but-2-en-1-one

S13

Yield: 45% (60 mg); pale yellow oil. 1H NMR (400M Hz, CDCl3) δ (ppm): 7.92 (d, J = 8.0 Hz, 2 H), 7.46 (d, J = 7.4 Hz, 2 H), 7.28 (d, J = 8.0 Hz, 2 H), 7.18 (m, 3 H), 6.80 (d, J = 15.7 Hz, 1H), 6.38-6.30 (m, 1 H), 3.91 (d, J = 6.8 Hz, 2 H), 2.68 (q, J = 7.6 Hz, 2 H), 2.42 (s, 3 H), 1.18 (t, J = 7.6 Hz, 3 H); 13C NMR (100 MHz, CDCl3), δ = 197.7, 144.0, 141.3, 135.6, 134.2, 131.2, 129.3, 128.6, 128.5, 127.6, 126.1, 126.0, 124.3, 43.0, 26.3, 21.6, 15.3; IR (KBr): 3028, 1674, 1607, 1260, 1178, 784 cm-1; HRMS (ESI) Calcd for C19H20O [M] + Na+ = 287.1406, Found =287.1404.

4e. (E)-4-(2-methoxyphenyl)-1-(p-tolyl)but-2-en-1-one

Yield: 65% (86 mg); pale yellow oil. 1H NMR (400M Hz, CDCl3) δ (ppm): 7.90 (d, J = 8.1 Hz, 2 H), 7.45 (dd, J = 7.6 Hz, J = 1.4 Hz, 2 H), 7.27 (d, J = 8.3 Hz, 2 H), 7.22-7.18 (m, 1 H), 6.92-6.84 (m, 3 H), 6.50-6.43 (m, 1 H), 3.90 (dd, J = 6.9 Hz, J = 1.4 Hz, 2 H), 3.84 (s, 3 H), 2.42(s, 3H); 13C NMR (100 MHz, CDCl3) δ (ppm): 197.8, 156.5, 143.9, 134.3, 129.3, 128.5, 128.4, 128.2, 126.9, 126.2, 123.4, 120.7, 110.8, 55.5, 43.2, 21.6; IR (KBr): 2956, 1671, 1599, 1488, 1243, 1024 cm-1; C18H18O2 [M] + Na+ = 289.1200, Found = 289.1202.

4f. (E)-1-(p-tolyl)pent-2-en-1-one

Yield: 60% (52 mg); pale yellow oil; 1H NMR (400M Hz, CDCl3): δ = 7.84 (d, J = 8.2 Hz, 2 H), 7.26 (d, J = 7.9 Hz, 2 H), 7.13 – 7.06 (m, 1H), 6.87 (td, J = 15.4 Hz, J = 1.6 Hz, 1 H), 2.42 (s, 3 H), 2.38-2.30 (m, 3 H) 1.14 (t, J = 7.4 Hz, 3 H);

13

C NMR

(100 MHz, CDCl3), δ = 190.6, 150.7, 143.3, 135.5, 129.2, 128.7, 124.9, 25.9, 21.6,

S14

12.4. IR (KBr): 3113, 2920, 1733, 1503, 1389, 1255, 1192, 751 cm-1. C12H14O [M] + Na+ = 197.0937, Found = 197.0932.

4g. (E)-4-cyclohexyl-1-(p-tolyl)but-2-en-1-one

Yield: 56% (68 mg); pale yellow oil. 1H NMR (400M Hz, CDCl3) δ (ppm): 7.84 (d, J = 8.2 Hz, 2 H), 7.26 (d, J = 7.9 Hz, 2 H), 7.08-7.00 (m, 1 H), 6.85 (td, J = 15.3 Hz, J = 1.2 Hz, 1 H), 2.41 (s, 3 H), 2.22-2.18(m, 2 H), 1.77-1.63 (m, 5 H), 1.51 – 1.46 (m, 1 H), 1.29-1.13 (m, 3H), 1.02-0.92 (m, 2H);

13

C NMR (100 MHz, CDCl3) δ (ppm):

190.3, 148.4, 143.3, 135.5, 129.2, 128.7, 126.9, 40.8, 37.5, 33.2, 26.4, 26.2, 21.6; IR (KBr): 3028, 1668, 1610, 1446, 1263, 1016, 805 cm-1; C17H22O [M] + H+ = 243.1743, Found = 243.1739.

4h. (E)-1-(p-tolyl)non-2-en-1-one

Yield: 43% (50 mg); pale yellow oil. 1H NMR (400M Hz, CDCl3) δ (ppm): 7.84 (d, J = 8.2 Hz, 2 H), 7.26 (d, J = 8.0 Hz, 2 H), 7.09-7.02 (m, 1 H), 6.87 (td, J = 15.4 Hz, J = 1.3 Hz), 2.41 (s, 3 H), 2.33-2.28 (m, 2 H), 1.55-1.48 (m, 2 H), 1.37-1.28 (m, 6 H), 0.89 (t, J = 6.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 190.5, 149.6, 143.3, 135.5, 130.2, 129.2, 128.7, 125.8, 32.8, 31.6, 28.9, 28.2, 22.6, 21.6, 14.1; IR (KBr): 2970, 1696, 1649, 1538, 1451, 1041 cm-1; C16H22O [M] + Na+ = 253.1559, Found = 253.1559.

4i. 3-methyl-1-(p-tolyl)but-2-en-1-one

S15

Yield: 84% (73 mg); pale yellow oil. 1H NMR (400M Hz, CDCl3) δ (ppm): 7.83 (d, J = 8.2 Hz, 2 H), 7.23 (d, J = 8.0 Hz, 2 H), 6.72 (t, J = 1.2 Hz, 1 H), 2.39 (s, 3 H), 2.19 (d, J = 0.8 Hz, 3 H), 2.00 (d, J = 0.9 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 190.3, 154.8, 141.9, 135.7, 128.1, 127.3, 120.2, 26.9, 20.5, 20.1; IR (KBr): 2961, 1660, 1610, 1254, 1013, 805 cm-1; HRMS (ESI) Calcd for C12H14O [M] + Na+ = 197.0937, Found = 197.0933.

4j. 4-methyl-1-(p-tolyl)pent-3-en-1-one

pale yellow oil; 1H NMR (400M Hz, CDCl3) δ (ppm): 7.87 (d, J = 8.2 Hz, 2 H), 7.26 (d, J = 7.9 Hz, 2 H), 5.45 – 5.41 (m, 1 H), 3.66 (d, J = 6.9 Hz, 2 H), 2.41 (s, 3 H), 1.76 (d, J = 1.1 Hz, 3 H), 1.69 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm) 198.3, 143.7, 135.3, 134.4, 129.2, 128.4, 116.5, 38.4, 25.8, 21.6, 18.2; IR (KBr): 2975, 1665, 1604, 1503, 1293, 1179, 816 cm-1; HRMS (ESI) Calcd for C13H16O [M] + Na+ = 211.1093, Found = 211.1107.

4f-a. (Z/E)-1-(p-tolyl)pent-3-en-1-one

pale yellow oil; 1H NMR (400M Hz, CDCl3) δ (ppm): 7.89 (m, 2 H), 7.28 (m, 2 H), 5.75-5.61 (m, 2 H), 3.76-3.67 (m, 2 H), 2.43 (s, 3 H), 1.75-1,67 (m, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm) 198.4, 197.9, 143.8, 134.3, 134.2, 129.4, 129.3, 128.5, 128.4, 127.4, 123.6, 122.5, 42.4, 37.1, 21.7, 18.2, 13.2; IR (KBr): 3036, 1668, 1607, 1279, 1018, 810 cm-1; HRMS (ESI) Calcd for C12H14O [M] + Na+ = 197.0937, Found = 197.0932.

4k. (E)-7-oxo-7-(p-tolyl)hept-5-en-1-yl acetate

S16

Yield: 52% (67 mg); pale yellow oil; 1H NMR (400M Hz, CDCl3) δ (ppm): 7.85 (d, J = 8.1 Hz, 2 H), 7.27 (d, J = 7.1 Hz, 2 H), 7.07-7.00 (m, 1 H), 6.90 (d, J = 15.4 Hz), 4.09 (t, J = 6.3 Hz, 2 H), 2.42 (s, 3 H), 2.36 (q, J = 7.0 Hz, 2 H), 2.06 (s, 3 H), 1.72-1.67 (m, 4 H); 13C NMR (100 MHz, CDCl3) δ (ppm) 198.3, 143.7, 135.3, 134.4, 129.2, 128.4, 116.5, 38.4, 25.8, 21.6, 18.2; IR (KBr): 2989, 1732, 1662, 1615, 1235, 1038 cm-1; HRMS (ESI) Calcd for C16H20O3 [M] + Na+ = 283.1305, Found = 283.1296.

4l. (E)-4, 8-dimethyl-1-(p-tolyl) nona-3, 7-dien-1-one

Yield: 40% (51 mg); pale yellow oil; 1H NMR (400M Hz, CDCl3) δ (ppm): 7.87 (d, J = 8.2 Hz, 2 H), 7.26 (d, J = 7.9 Hz, 2 H), 5.46-5.41 (m, 1 H), 5.08-5.05 (m, 1 H), 3.67 (d, J = 6.8 Hz, 2 H), 2.41 (s, 3 H), 2.08 (m, 4 H), 1.69 (s, 3 H), 1.64 (s, 3 H), 1.58 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ (ppm): 198.3, 143.7, 138.8, 134.4, 131.6, 129.2, 128.5, 124.0, 116.4, 39.7, 38.4, 26.5, 25.6, 21.6, 17.7, 16.6; IR (KBr): 2981, 1676, 1610, 1285, 1105, 813 cm-1; HRMS (ESI) Calcd for C18H24O [M] + H+ = 257.1890, Found = 257.1893. 7. References Entry

Products

Reference

1

3a

[S1]

2

3b

[S1]

3

3f

[S1]

4

3g

[S1]

5

3h

[S1] S17

6

3i

[S1]

7

3o

[S1]

8

3p

[S1]

9

3m

[S2]

[S1] F. Manjolinho, M. F. Grünberg, N. Rodrí guez, L. J. Gooßen, Eur. J. Org. Chem. 2012, 2012, 4680-4683; [S2] N. Rodríguez, F. Manjolinho, M. F. Grünberg, L. J. Gooßen, Chem. Eur. J. 2011, 17, 13688-13691.

S18

8. Copies of the 1H NMR and 13C NMR spectra of products 3a. (E)-1-(p-tolyl)but-2-en-1-one

5

4

1.989 1.972

3

2

1

0

ppm

200

190

180

170

160

150

140

130

120

110

100

S19

90

80

70

21.620 18.550

77.328 77.011 76.693

135.350 129.203 128.655 127.477

144.429 143.362

C NMR (100 MHz, CDCl3) 190.255

13

6

2.99

7

3.06

8

2.48 0.96 1.00

9

2.00

10

2.401

H NMR (400 MHz, CDCl3)

7.840 7.819 7.259 7.246 7.239 7.094 7.077 7.060 7.039 7.022 7.005 6.917 6.878

1

60

50

40

30

20

10

0

ppm

200

180

160

140 7 6

120 5

100

S20 4

80

18.574

8

3.12

9 1.01 2.00 0.99 1.00

2.00

10

77.363 77.046 76.728

13 11

137.943 132.565 128.496 127.569

12

145.002

2.005 1.988

7.933 7.913 7.565 7.546 7.529 7.477 7.459 7.439 7.263 7.118 7.101 7.083 7.063 7.046 7.029 6.926 6.887

1

190.760

3b. (E)-1-phenylbut-2-en-1-one: H NMR (400 MHz, CDCl3)

3

60

2 1

40 0

20

-1

0

ppm

C NMR (100 MHz, CDCl3)

ppm

220

200

180

160

140 6 5

120 4

100

S21 3 2

80 1

60

0 -1

40 24.220 18.526 13.745

7

38.020

8

3.25

9 3.05

10 2.11

11

77.382 77.063 76.746

13 12 2.14 1.00 1.00

13

135.584 128.641 128.612 127.504

2.03

2.732 2.713 2.694 2.676 1.997 1.994 1.980 1.977 1.276 1.257 1.238

7.876 7.855 7.292 7.271 7.106 7.089 7.072 7.068 7.056 7.051 7.034 7.018 6.931 6.927 6.893 6.889

1

148.029 144.372

190.261

3c. (E)-1-(4-ethylphenyl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

-2

20

-3 -4

0 ppm

C NMR (100 MHz, CDCl3)

ppm

220

200

180

160

140

120

100

S22 3 2

80 1

60

0

40 24.220 18.526 13.745

4

38.020

5 3.17

6 2.11

7

3.07

2.11

8

77.382 77.063 76.746

9

135.584 128.641 128.612 127.504

13 10

148.029 144.372

11 2.21 1.00 1.02

2.02

2.656 2.637 2.618 1.993 1.989 1.976 1.972 1.707 1.689 1.670 1.651 1.632 1.614 0.961 0.943 0.924

7.869 7.849 7.268 7.247 7.106 7.088 7.072 7.050 7.033 7.017 6.932 6.928 6.893 6.890

1

190.261

3d. (E)-1-(4-propylphenyl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

-1

20

-2

0

ppm

C NMR (100 MHz, CDCl3)

ppm

220

200

180

160

140

120 4

100

S23 3

80 2

60

40 18.583

5 9.27

6

35.079 31.119

3.00

7

77.366 77.048 76.730

135.262 128.495 127.503 125.470

1.04 0.96

8

144.478

13 9 2.03

10

156.322

2.00

1.343

2.001 1.984

7.892 7.871 7.488 7.467 7.260 7.113 7.096 7.079 7.060 7.058 7.041 7.024 6.935 6.896

1

190.289

3e. (E)-1-(4-(tert-butyl)phenyl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

1 0

20

-1

0 ppm

C NMR (100 MHz, CDCl3)

ppm

200

180

160 7

140 6

120 5

100

S24

80 18.618

8

3.03

1.00 1.01

9

77.368 77.254 77.050 76.733

13 10 2.04 2.02 3.09

2.00

11

145.349 144.910 140.002 136.626 129.130 128.945 128.156 127.474 127.275 127.190

2.021 2.017 2.004 2.000

8.018 7.997 7.691 7.670 7.633 7.615 7.480 7.476 7.462 7.443 7.406 7.393 7.388 7.382 7.369 7.153 7.136 7.119 7.115 7.098 7.080 7.064 6.973 6.969 6.935 6.931

1

190.170

3f. (E)-1-([1,1'-biphenyl]-4-yl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

4 3

60 2

40 1

20

0 ppm

C NMR (100 MHz, CDCl3)

0

ppm

200

180

160

140

120 5.5 5.0

100

S25 4.5

80 2.97

6.0 4.0 3.5

60 18.521

3.01

6.5

55.437

7.0

77.376 77.058 76.741

7.5

113.724

8.0

1.14 3.03

8.5

130.776 127.151

13 9.0

143.874

2.00

9.5

163.269

1.983 1.980 1.966 1.963

3.852

7.946 7.924 7.260 7.090 7.073 7.056 7.052 7.035 7.018 7.001 6.941 6.928 6.925 6.919 6.891 6.887

1

188.947

3g. (E)-1-(4-methoxyphenyl)but-2-en-1-one H NMR (400 MHz, CDCl3)

3.0

40

2.5 2.0

C NMR (100 MHz, CDCl3)

20

1.5 ppm

0

ppm

13

200

180

160

140

7

C NMR (100 MHz, CDCl3) 6 5

120

100

S26

80 3

60

40 -0.009

4

18.639

77.338 77.224 77.020 76.702

3.09

8 1.00 1.02

9 2.02

10

145.638 139.018 136.208 129.924 128.831 127.072

2.04

2.018 2.014 2.001 1.997 1.615

7.883 7.861 7.450 7.428 7.265 7.134 7.117 7.100 7.096 7.079 7.062 7.045 6.893 6.889 6.855 6.851

1

189.392

3h. (E)-1-(4-chlorophenyl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

2 1 ppm

20

0

ppm

200

180

160 6.5

140 6.0

120 5.5 5.0

100

S27 4.5

80 4.0 3.5

60

3.0

40

2.5 3.07

7.0

3.06

7.5

21.351 18.549

8.0 1.03 1.02

8.5

77.328 77.011 76.693

13 9.0

144.756 138.309 137.989 133.338 129.036 128.343 127.718 125.706

9.5 2.01

2.00

2.416 2.007 2.004 1.990 1.987

7.737 7.725 7.721 7.709 7.705 7.370 7.359 7.342 7.323 7.260 7.107 7.090 7.073 7.069 7.051 7.034 7.018 6.919 6.915 6.881 6.877

1

190.967

3i. (E)-1-(m-tolyl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

2.0

20

1.5 ppm

C NMR (100 MHz, CDCl3)

0

ppm

200

180

160

140

120

100

S28

80 4.0 3.5

60 3.0

40 -0.004

4.5 3.10

5.0

18.609

5.5

55.456

3.23

6.0

77.335 77.221 77.018 76.700

6.5

129.462 127.571 121.100 119.161 112.832

7.0

139.323

1.00

7.5

145.097

13 8.0 2.00

8.5

159.825

2.02 1.10

2.006 2.002 1.989 1.985

3.858

1

190.507

7.506 7.487 7.463 7.458 7.384 7.364 7.345 7.264 7.120 7.107 7.103 7.086 7.082 7.065 7.048 7.031 6.908 6.904 6.869 6.866

3j. (E)-1-(3-methoxyphenyl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

2.5 2.0 1.5 ppm

C NMR (100 MHz, CDCl3)

20

0

ppm

200

180 7.0

160 6.5

140 6.0

120 5.5 5.0

100

S29 4.5 4.0

80 3.5 3.0

60 2.5

40

3.07

6.26

7.5

1.05 1.15 1.03

8.0

21.227 18.521

8.5

77.395 77.077 76.759

13 9.0

144.495 138.113 138.049 134.239 127.817 126.293

9.5 2.00

2.362 1.992 1.988 1.975 1.972

7.526 7.172 7.090 7.072 7.055 7.051 7.034 7.017 7.000 6.908 6.904 6.870 6.866

1

191.067

3k. (E)-1-(3,5-dimethylphenyl)but-2-en-1-one H NMR (400 MHz, CDCl3)

2.0 1.5

20

1.0 ppm

C NMR (100 MHz, CDCl3)

0

ppm

200

180

160

7.0 6.5

140

6.0

120

5.5 5.0

100

S30 4.5 4.0

80

3.5

20.037 18.489

7.5 3.0

60

2.5

40

3.11

8.0 3.07

8.5 1.01

9.0

77.373 77.055 76.737

13 9.5 1.00

2.04 2.02

10.0

146.726 138.995 136.631 132.411 131.121 130.155 127.944 125.266

1.952 1.935

2.378

7.376 7.357 7.327 7.309 7.262 7.235 7.216 7.197 6.767 6.750 6.732 6.712 6.694 6.677 6.519 6.480

1

196.926

3l. (E)-1-(o-tolyl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

2.0 1.5

20

1.0 0.5

0

ppm

C NMR (100 MHz, CDCl3)

ppm

200

180

160 7

140 6

120 5

100

S31

80 17.512

8 3.10

1.01 1.03 1.07 1.10 1.00 1.01

9

76.313 76.197 75.995 75.678

13 10

144.687 132.567 132.481 130.139 130.085 129.759 129.731 126.062 125.923 123.348 123.313 115.497 115.268

11

161.183 158.668

1

188.606 188.584

7.714 7.709 7.695 7.690 7.676 7.672 7.509 7.505 7.497 7.491 7.489 7.486 7.484 7.478 7.476 7.473 7.471 7.465 7.457 7.453 7.259 7.237 7.234 7.218 7.215 7.199 7.196 7.142 7.140 7.122 7.119 7.116 7.113 7.095 7.093 7.029 7.024 7.011 7.007 7.003 6.990 6.986 6.973 6.969 6.770 6.766 6.762 6.758 6.754 6.750 6.727 6.723 6.720 6.716 1.988 1.984 1.971 1.967 1.603

3m. (E)-1-(2-fluorophenyl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

4 3

60 2

40 1

20

ppm

C NMR (100 MHz, CDCl3)

0

ppm

200

180

160 6

140 5

120

100

S32 4

80 18.629

7 3.11

1.00

8

77.397 77.079 76.761

13 9 1.00

10

147.984 138.982 132.047 131.052 131.028 130.131 128.994 126.637

4.16

1.970 1.966 1.952 1.949

1

194.248

7.400 7.398 7.396 7.388 7.383 7.372 7.366 7.362 7.360 7.355 7.347 7.342 7.337 7.327 7.323 7.316 7.311 7.308 7.304 7.292 7.288 7.276 6.764 6.747 6.729 6.724 6.712 6.707 6.690 6.673 6.503 6.499 6.464 6.460

3n. (E)-1-(2-chlorophenyl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

3

60

2

40 1

20

0

0 ppm

C NMR (100 MHz, CDCl3)

ppm

200

180

160

140 6.0

120 5.5 5.0

100

S33 4.5

80 4.0 3.5

60

3.0 2.5

40

2.0

20

1.5

1.015 -0.011

6.5 3.26

7.0

18.420

7.5

77.359 77.245 77.041 76.724

8.0 1.03

8.5

133.595 131.758 128.115 126.944

13 9.0 2.15

9.5

145.108 144.210

1.05 1.00

1.993 1.976

7.750 7.741 7.637 7.625 7.257 7.166 7.145 7.133 7.123 7.111 7.094 7.077 6.841 6.804

1

182.185

3o. (E)-1-(thiophen-3-yl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

1.0

0

ppm

C NMR (100 MHz, CDCl3)

ppm

200

180

160 7.5 7.0

140 6.5 6.0

120 5.5 5.0

100

S34 4.5

80 4.0

18.566

8.0

3.14

8.5 1.04 1.00

9.0

77.383 77.267 77.065 76.748

13 9.5

146.946 136.907 133.791 132.771 131.272 130.509 128.374 127.267 126.928 126.374 125.646 124.406

10.0 1.04 1.05 1.05 3.13

1.01

1.978 1.962

8.257 8.238 7.961 7.940 7.892 7.874 7.661 7.644 7.565 7.551 7.533 7.519 7.508 7.489 7.470 7.261 6.902 6.885 6.867 6.846 6.829 6.812 6.700 6.661

1

196.138

3p. (E)-1-(naphthalen-1-yl)but-2-en-1-one: H NMR (400 MHz, CDCl3)

3.5

60

3.0 2.5

40

2.0 1.5

20

1.0

0

ppm

C NMR (100 MHz, CDCl3)

ppm

220

200

180

160

140 6.0

120 5.5

100

S35 5.0 4.5

80 4.0

60 3.37

6.5 3.5 3.0

40 21.657

7.0

42.654

7.5

2.04

8.0

1.93

8.5

77.354 77.035 76.719

13 9.0 2.04 5.60

9.5

144.043 137.075 134.183 133.434 129.366 128.509 128.488 127.445 126.287 122.846

2.00

2.411

3.883 3.868

7.912 7.891 7.382 7.364 7.309 7.305 7.291 7.278 7.273 7.258 7.246 7.226 7.213 7.208 7.190 6.560 6.520 6.498 6.483 6.467 6.443 6.427

1

197.607

4b. (E)-4-phenyl-1-(p-tolyl)but-2-en-1-one H NMR (400 MHz, CDCl3)

2.5

20

2.0 1.5

0 ppm

C NMR (100 MHz, CDCl3)

ppm

200

190

180 7.5

170 7.0

160

150 6.5

140 2.03

8.0

2.00

8.5 6.0

130

120 77.356 77.039 76.721

13 144.029 138.047 137.004 134.183 133.510 129.361 128.500 128.407 128.247 126.961 123.487 122.604

9.0 2.15 3.18 1.08

2.08

5.5

C NMR (100 MHz, CDCl3)

110 4.5

100

90

S36

80 3.5

70

60

3.0

50

2.5

40 21.662 21.372

4.0

3.49 3.66

5.0

42.692

2.424 2.337

3.887 3.873

7.924 7.904 7.290 7.270 7.260 7.212 7.198 7.184 7.049 7.035 6.543 6.503 6.491 6.476 6.461 6.436

1

197.685

4c. (E)-4-(m-tolyl)-1-(p-tolyl)but-2-en-1-one H NMR (400 MHz, CDCl3)

2.0

30

1.5

20

10

ppm

ppm

200

180

160

140

120

100

S37

80

60

40

2

20 15.291

26.352 21.650

3 3.50

4

43.033

5 3.29

6 2.19

7 2.07

1.00

1.08

8

77.333 77.015 76.698

13

143.991 141.284 135.609 134.190 131.164 129.342 128.568 128.510 127.592 126.126 126.067 124.275

9 1.11 2.12 3.09

2.07

1.577 1.197 1.178 1.159

2.710 2.691 2.672 2.654 2.423

3.922 3.905

7.930 7.910 7.473 7.454 7.289 7.269 7.259 7.187 7.166 7.149 7.135 6.819 6.779 6.377 6.360 6.342 6.321 6.304

1

197.682

4d. (E)-4-(2-ethylphenyl)-1-(p-tolyl)but-2-en-1-one H NMR (400 MHz, CDCl3)

1 0 ppm

C NMR (100 MHz, CDCl3)

0

ppm

200

180

160

140

120

100

S38 4.5

80 4.0 3.5

60

3.0

40

2.5

20

-0.013

5.0 3.24

5.5

21.642

6.0

43.213

6.5

55.464

2.23 3.08

7.0

77.323 77.208 77.005 76.688

1.00

3.22

7.5

143.897 134.272 129.306 128.493 128.466 128.213 126.850 126.185 123.435 120.664 110.814

156.494

13 8.0

2.70 1.21

8.5 1.08

2.07

2.415

3.916 3.913 3.899 3.895 3.837

1

197.826

7.920 7.900 7.466 7.462 7.447 7.443 7.279 7.258 7.224 7.220 7.204 7.185 7.181 6.925 6.907 6.898 6.889 6.861 6.842 6.503 6.486 6.468 6.463 6.446 6.428

4e. (E)-4-(2-methoxyphenyl)-1-(p-tolyl)but-2-en-1-one H NMR (400 MHz, CDCl3)

2.0 ppm

C NMR (100 MHz, CDCl3)

0

ppm

220

200

180

160

140

120

100

S39 3

80 2

60

1

40

0

20 1.013 -0.013

4

12.385

5

25.893 21.623

6 3.00

3.15 2.16

7

77.326 77.211 77.009 76.691

135.471 129.195 128.671 124.952

8

143.342

13 9 2.54 1.13 1.08

10

150.742

2.06

2.415 2.375 2.358 2.340 2.322 2.306 1.613 1.160 1.141 1.123

7.855 7.835 7.273 7.254 7.134 7.118 7.101 7.096 7.079 7.064 6.892 6.854

1

190.602

4f. (E)-1-(p-tolyl)pent-2-en-1-one H NMR (400 MHz, CDCl3)

-1

0

ppm

C NMR (100 MHz, CDCl3)

ppm

200

180

160

140

120

100

S40 3.5 3.0

80 2.5

60 -0.009

4.0 2.0 1.5 2.08

4.5 3.38

5.0 1.14

5.5 5.22

6.0

40.813 37.487 33.248 26.361 26.226 21.623

6.5 2.01

3.06

7.0

77.339 77.223 77.020 76.703 67.096

7.5

135.481 129.193 128.669 126.862

148.370 143.321

13 8.0 1.01 1.00

8.5 2.45

2.00

1

190.347

7.850 7.830 7.271 7.261 7.252 7.075 7.056 7.037 7.018 7.000 6.874 6.871 6.868 6.836 6.833 6.830 2.414 2.223 2.220 2.204 2.188 2.185 1.766 1.761 1.758 1.727 1.709 1.706 1.699 1.691 1.675 1.668 1.664 1.633 1.514 1.505 1.497 1.488 1.480 1.469 1.460 1.259 1.235 1.228 1.222 1.204 1.196 1.192 1.185 1.170 1.163 1.155 1.132 1.019 1.012 0.981 0.952 0.929 0.920

4g. (E)-4-cyclohexyl-1-(p-tolyl)but-2-en-1-one H NMR (400 MHz, CDCl3)

1.0

40

0

20

0.5 0.0 ppm

C NMR (100 MHz, CDCl3)

ppm

200

180

160

140

120 4 3

100

S41

80 2

60 2.96

5

32.847 31.630 28.927 28.192 22.560 21.622 14.058

6 2.02 6.60

7

3.22 1.97

8

77.332 77.014 76.697

9

143.327 135.473 130.184 129.190 128.897 128.669 125.820

13 149.605

10 2.63 0.94 0.93

1.97

2.415 2.336 2.317 2.299 2.282 1.554 1.536 1.518 1.500 1.481 1.373 1.351 1.334 1.308 1.255 0.910 0.893 0.876

7.853 7.833 7.713 7.693 7.273 7.261 7.253 7.091 7.074 7.053 7.035 7.018 6.892 6.853

1

190.494

4h. (E)-1-(p-tolyl)non-2-en-1-one H NMR (400 MHz, CDCl3)

1 0

40

-1

20

ppm

C NMR (100 MHz, CDCl3)

O C6H13

0

ppm

4i. 3-methyl-1-(p-tolyl)but-2-en-1-one 2.393 2.195 2.193 2.001 1.999 6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

ppm

2.95

6.5

220

200

180

160

140

120

100

S42

80

26.869 20.537 20.063

76.344 76.027 75.709

135.694 128.083 127.296 120.245

141.883

154.808

C NMR (100 MHz, CDCl3) 190.179

13

7.0

2.96

7.5

3.00

8.0

0.98

8.5

2.16

9.0

2.03

9.5

7.259 7.244 7.223 6.728 6.725 6.722

H NMR (400 MHz, CDCl3) 7.844 7.824

1

60

40

20

0

ppm

200

180

160

140

120

100

S43 4.5 4.0

80 3.5

60

3.0 2.5

40

3.08 3.08

5.0

25.790 21.621 18.185

5.5

3.10

6.0

38.397

6.5 2.06

7.0

77.329 77.012 76.694

7.5 1.00

8.0

116.523

8.5

135.334 134.392 129.239 128.422

13 9.0

143.699

9.5 2.68

2.05

1.766 1.763 1.697 1.582

2.411

3.669 3.652

5.454 5.451 5.447 5.440 5.437 5.433 5.430 5.426 5.420 5.416 5.412

7.267 7.261 7.247

7.879 7.859

1

198.330

4j. 4-methyl-1-(p-tolyl)pent-3-en-1-one H NMR (400 MHz, CDCl3)

2.0 1.5

20

1.0

0

ppm

C NMR (100 MHz, CDCl3)

ppm

210

200

190

180

170 7.0

160 6.5

150

140 6.0

130 5.5

120 5.0

110 4.5

100

S44

90 4.0

80 3.00

7.5

2.03

8.0

1.95

8.5

77.367 77.049 76.731

13 143.843 134.264 134.182 129.407 129.277 128.457 128.410 127.393 123.632 122.494

9.0

2.18

2.00

3.5

C NMR (100 MHz, CDCl3)

70

2.5

60

50

40 21.664 18.156 13.221

3.16

3.0

42.423 37.135

1.746 1.743 1.731 1.729 1.716 1.665

2.432

7.898 7.891 7.878 7.287 7.284 7.274 7.268 5.749 5.747 5.741 5.740 5.736 5.734 5.721 5.718 5.716 5.712 5.708 5.696 5.693 5.678 5.675 5.661 5.646 5.630 5.622 5.607 3.755 3.747 3.744 3.742 3.688 3.672

1

198.380 197.930

4f-a. (Z/E)-1-(p-tolyl)pent-3-en-1-one H NMR (400 MHz, CDCl3)

2.0 1.5

30

20

1.0

10

ppm

0 ppm

200

180

160

140

120

100

S45

80

60

2 1

40

20

-0.004

32.289 28.173 24.633 21.650 20.992

4.18

3 3.37

4

3.27 2.23

5

64.087

6

77.335 77.221 77.017 76.700

2.39

7

135.320 129.247 128.678 126.208

1.04 1.00

8

148.388 143.506

13 2.20

9

171.180

2.11

2.421 2.383 2.365 2.347 2.331 2.059 1.722 1.702 1.685 1.669

4.109 4.093 4.077

7.858 7.837 7.282 7.264 7.074 7.056 7.035 7.018 7.001 6.921 6.883

1

190.240

4k. (E)-7-oxo-7-(p-tolyl)hept-5-en-1-yl acetate H NMR (400 MHz, CDCl3)

0 -1

0

ppm

C NMR (100 MHz, CDCl3)

ppm

200

180

160

140

120

100

S46 3.5

80 3.0

60

2.5

40

3.40 2.89 2.53

4.0 4.69

4.5

26.528 25.647 21.623 17.676 16.590

5.0

2.93

5.5

39.678 38.427

6.0 2.00

6.5 1.09

7.0 0.98

7.5

77.344 77.026 76.708

13 8.0

143.668 138.829 134.388 131.561 129.226 128.451 124.019 116.444

8.5 2.21

1.97

2.409 2.104 2.087 2.071 2.055 1.698 1.646 1.582

3.674 3.657

5.470 5.455 5.453 5.439 5.436 5.078 5.067 5.064 5.048

7.263 7.260 7.244

7.877 7.857

1

198.317

4l. (E)-4, 8-dimethyl-1-(p-tolyl) nona-3, 7-dien-1-one H NMR (400 MHz, CDCl3)

2.0 1.5

20

1.0 ppm

C NMR (100 MHz, CDCl3)

0

ppm

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