Institut Parisien de Chimie Moléculaire, UMR 7201. Institut de Chimie ... Si. Si. 40
- 50%. 5-exo-dig. Si. O. Si. X. 5-exo-trig and 5-exo-dig. X = SPh, SO2Ph, SOPh ...
Institut Parisien de Chimie Moléculaire, UMR 7201 Institut de Chimie Moléculaire, FR 2769
MÉTAUX & RADICAUX, DE PRÉCIEUX OUTILS EN SYNTHÈSE ORGANIQUE
LOUIS FENSTERBANK
Mardis de la Chimie 15 mai 2012
Our Approach in Organic Synthesis! PRECURSORS
TARGETS MULTI-EVENTS REACTIONS
- polycyclic derivatives
- preorganized systems
- natural products or analogs
- polyunsaturated substrates
- physically or biologically relevant molecules
- modular and accessible - efficiency - selectivity (chemo-, regio-, stereo-) - eco-compatible processes
radical processes:
.
.
S,P,B
organometallic catalysis:
.
- use of hydrogen transfers, !-elimination, homolytic substitution - forbidden processes - new partners (heteroatoms)
M
Pt
Au
One-Pot Synthesis of a Linear Triquinane
CN Bu3SnH, AIBN
O Si
SO2Ph Br
CN
10 elementary radical steps
Si Formation of :
O Si
Si
- 5 C-C bonds - 3 contiguous quaternary centers
50%
- 4 stereogenic centers
!-CN : "-CN, 90 : 10
J. Org. Chem. 1998, 63, 6764.
Mechanism CN O Si
Si
Bu3SnH, AIBN
X
O
Br
10 equiv.
Si
Si
CN
X = SPh, SO2Ph, SOPh
40- 50%
!-elimination
5-exo-dig
-X
O Si Si
CN
5-exo-trig
O
Si
Si
CN
CN
X
X
.
[3 + 2] and 5-exo-dig
Si O
Si
X 1,5-H transfer
Si
O
X H Si
Cyanamides as New Partners for Radical Cascades
N
R
R
N N
N
O N
O
Bu3SnH, AIBN
N N
N
O N
O
O
71%
S
N
N N
amide-iminyl radical
N 99%
CN
N 57%
Total Synthesis of Luotonin A
O
O
4 steps N
Cl 56 %
N3 N
I
2 steps 46 %
N H
N
I
NaH, BrCN O N
Isolated from Peganum nigellastrum, a Chinese medicinal plant
N
I
N
air, pyr. PhH, h!
O N
Inhibitor of topoisomerase I
N N
luotonin A 54%
Chem. Eur J. 2008,14, 1238-52.
Alkyl Radicals - Cyclizations
R1 R2 PhSe
Bu3SnH
O n
N
O
(slow addition) AIBN (1.5 equiv.)
Ph
PhH, !, 3 h
N O
N n
R1 R 2
O
O
N
N
N N
N
N
Deoxyvasicinone, 65%
N
!-Methyldeoxyvasicinone, 76%
!,!-Dimethyldeoxyvasicinone, 87%
O N
Adhatoda vasica
N
Mackinazolinone, 51%
Mackinlaya subulata
Vinyl Radicals O
Bu3SnH AIBN (1.5 equiv.)
O
I N
N
PhH, !
N
N
66%
reduction of the olefin ! O
Bu3SnD AIBN (1.5 equiv.)
O
I N
N
PhH, !
N
55%
O
I
D D
N N
N
D
D
D D
O
Bu3SnH AIBN (1.5 equiv.)
D D
N
PhH, !
N D
48%
D D
Possible Mechanism O
O
O
I
?
N
N
N
H
N
H• +
O N
N N
H
N
N N
N H SnBu3
H
O
O
O
Path B bimolecular transfer
N
O
O
N
H
H
N
Path A β-elimination
N
N
H N N O
N
+
H
N H SnBu3
Double Tagging
O
O
I
N
N N
OMe
H
+ O
I
Bu3SnH AIBN
N D
N H
N D
O D
13%
the reduction is an intermolecular process
D D
N N
D D
OMe 12%
D
N
D D
OMe 11%
O
D D
N
t-BuOH, !
D
N N
O
H
D D
14%
Can We Transfer Other Groups ?
O
I N N
O N
?
N R
O
R
N N R
Can We Transfer Other Groups ?
O
I N
N Me
O
Me
Bu3SnH (2 equiv.) AIBN (1.5 equiv.)
N
O
N
+
N
PhH, reflux
I
O
Me
Me
45% O
i-Pr
N N
O
O N
N N
52%
i-Pr
H
N
t-BuOH H
69%
N N
34%
N
I
+
N
i-Pr
N i-Pr
O
Me
Me
Can We Transfer Other Groups ? O
I
O
CF3
N
N t-BuOH N F3C
O
I N N
F
F
CF3
N
CF3
55%
O
Bu3SnH (2 equiv.) AIBN (1.5 equiv.) PhH, reflux
F
N N
30%
J. Am. Chem. Soc. 2010, 132, 4381
Enantiomers ?
Addition of Radicals onto Vinylsulfoxides
sulfoxide:
R
S
O
Michael addition
O
S*
R'
R'
R1
OS+ R2
anti Michael addition
R
Zahouily, M.; Journet, M.; Malacria, M. Synlett 1994, 366. Lacôte, E.; Malacria, M. C. R. Acad. Sci. Fr., Ser. IIc 1998, 191. recent work: Lee, E. et al. J. Am. Chem. Soc. 2005, 127, 10396.
O S R
!-elimination
R'
R
Addition of Radicals onto Vinylsulfoxides
Bu3SnH, Et3B/O2 toluene, 0ºC
E
R +
E Tol-
S
O
93%
H
E E
S, > 98% ee
OMe
PhSe E E MeO OS* with MAD S*O = E = CO2Me
S O
H E Tol
t-Bu
MAD = MeAl
E S+
52%
E
OMe R, 92%ee
OLA
O t-Bu
R
E
2
J. Am. Chem. Soc. 1999, 121, 11395.
New Partners for Radical Asymmetric Synthesis
O p-Tol S
O S
p-Tol
R bis-p-tolylsulfinyl alkylidenes
O p-Tol S
O S
(S, S) pKa 20.9
p-Tol
1. BuLi, -78°C 2. RCHO
O p-Tol S R
O S
N p-Tol
OH
yield: 70-90%
O
NCN TsO
CuCl2 (cat.), MeCN
O p-Tol S R
O S
p-Tol
(S, S)
yield: 82-98%
review: Eur. J. Org. Chem. 2002, 3507. For cyclic bis-sulfoxides, see: Aggarwal, V. K. J. Org. Chem. 2003, 68, 4087 and references therein.
Bissulfoxides as Michael Acceptors Nu s-cis
O S O S !- stacking
R eclipsed lone pair
O S
O S
R
H Nu
Highly Diastereoselective Michael Additions
O p-Tol S
O S
O p-Tol N H
p-Tol
THF, -60°C
Ph
O S Ph
O S
O p-Tol
N
TFAA, pyridine
Ph
CH2Cl2
p-Tol O S
O S
O
MeO p-Tol
OMe Br
NaH, THF
MeOH
Ph
OMe N
(S)
O 30%
quant., 1 dias.
O
Hg(OAc)2
N O
O
O
S-pTol
p-Tol O S
O S
p-Tol CO2Me CO2Me
96%, 1 dias.
Synthesis of Succinate Natural Products O p-Tol
O
O
S
S
p-Tol
O p-Tol
O S
LDA, THF, -78°C
O S
p-Tol
11
2. LiOH, H2O2 n-Bu4NBr
11
11
79 %
O
COOH
1. TFAA, pyridine CH2Cl2
OAr
COOH 85 %
(+)-erythro-roccellic acid
Angew. Chem. Int. Ed. 2003, 42, 5342-45.
- first asymmetric synthesis, - active against tuberculosis
p-Tol
O S ( )7
O
O S
p-Tol
O
O
S
S
O
p-Tol
LDA, HMPA THF, -78°C
p-Tol p-Tol
( )7
O S
O S
1. TFAA, pyridine CH2Cl2
p-Tol
( )7 O
Ot-Bu 81% 1:1
O
Ot-Bu
2. LiOH, H2O2 n-Bu4NBr
COOH ( )7 28%
COOH
(+)-sphaeric acid
Synlett 2006, 713-716.
- unknown absolute configuration, - active against Staphylococcus aurus
Toward a Greener Radical Chemistry Two options:
New single electron transfer processes
New hydrogen donors
N N t-Bu
N Ph
RN
BH2 H
R
NR BH2 H
B–H = 85 kcal.mol-1
In collaboration with Prof. Dennis Curran, U. Pittsburgh
J. Am. Chem. Soc. 2008, 130, 10082. Rough estimate of the kinetics of redution: 4. to 8.104 M-1s-1 J. Am. Chem. Soc. 2009, 131, 11256 Org. Lett. 2010, 12, 3002
Ti Sm
+e R
Cu R E D O X
-e
Fe R
Visible Light-Induced Generation of Radicals Q
Principle:
Q - 0.86 V
RuIII(bpy)33+
Q
+ 0.84 V
Reductive quenching cycle
Oxidative quenching cycle
+1.29 V
- PMB esters - styrenes - phenols - sulfides
Q
Ru(bpy)32+*
RuI(bpy)3+
- 1.33 V
D
A RuII(bpy)32+
D
- activated halides - enones - azides - !-keto cyclopropanes - !-keto sulfoniums
A
What you need: Ru(bipy)3Cl2.(H2O)6 Seminal: Kellog, R. M. et al. Tetrahedron Lett. 1978, 1255; Pac, C. et al. J. Am. Chem. Soc. 1981, 103, 6495. Deronzier, A. et al. Tetrahedron Lett. 1984, 5517; Perkin Trans 2, 1984, 1093. MacMillan, D. W. C. et al. Science 2008, 322, 77; Yoon, T. P. et al. J. Am. Chem. Soc. 2008, 130, 12886; Stephenson, C. R. J. et al. J. Am. Chem. Soc. 2009, 131, 8756. Reviews: Narayanam, J. M. R.; Stephenson, C. J. R. Chem. Soc. Rev. 2011, 40, 102 Teply, F. Collect. Czech. Chem. Commun. 2011, 76, 859.
Objective: the Photoreduction of Epoxides E°(Rubpy32+/ Rubpy3+ ) = -‐‑1.33 V (vs SCE)
Objective:
Ru(bpy)3Cl2
O
E°< -‐‑ 2.0 V
R
R'
R
R'
Mismatching redox potentials
OH R'
R
via
O-
O
O
Ru(bpy)3Cl2
O
OH
Ph
Ph
Ph
Ph
via
O
-O
O Ph
O-
Ph
Ph
Ph
Can we use the radical generated ?
Precedent:
O O
Ph
+
N
1 mol% Ru(bpy)3Cl2 ! > 390 nm
N OH
E. Hasegawa et al. Tetrahedron 2006, 62, 658.
O
OH Ph
DMF, 3h
45% conversion, 70% NMR yield
Rearrangement also described with TiCp2Cl, see: E. Doris et al. J. Org. Chem. 2001, 66, 1046;
Scope of the Photoreductive Ring-Opening EtO2C
X R1
CO2Et
N H Hantzsch ester (1.1 equiv.) conditions A or B
O R2
XH
R2
R1
DMSO, lamp 14 W
R3
R3
OH O
OH O
R R = H, CO2Me, OMe, CF3, C4H4 Yield = 42 – 91% (cond. A)
Ts
94% (cond. A)
NH O
A = Ru(bpy)3Cl2.(H2O)6
O
B = Ir(dtbbpy)(ppy)2PF6 iPr2NEt (1.1 equiv.)
OH O
R' R = CO2Me, OMe, CF3 Yield = 54 – 89% (cond. A)
Ts
52% (cond. A)
NH O
OH
78% (cond. A)
87% (dr = 76:24) (cond. B)
Angew. Chem. Int. Ed. 2011, 50, 4463.
O
Mechanism Proposal OH O
HE HE
[ML3
Ph [ML3](n-1)+
]n+*
HE =
O
Ph
[ML3 EtO2C
O
]n+
H H CO2Et
Ph
Ph O
Ph HE
Path a: Reduction
O
EtO2C O
Ph
O
Ph
N Ph
Path b: C-C bond formation ?
N H
OH O Ph
Ph R
H
CO2Et
Allylations Me EtO2C
X R1
N H
R
O R2
+
SO2Tol
Ts
Ph EtO2C
NH O
Ph EtO2C 49%, dr > 95:5
DMSO, lamp 14 W
OH O
OH O
67%, dr = 96:4
XH O
Ir(dtbbpy)(ppy)2PF6 (5 mol%)
(3 equiv.)
Ph EtO2C
CO2Et
R2
OH O OMe
73%, dr = 93:7
Ts
R1 R
Ph EtO2C
EtO2C
51%, dr >95:5
NH O
Ph EtO2C
OH O OMe
46%, dr > 95:5
OH O
Ph Me 60%, dr = 90:10
70%, dr > 95:5
Ts
NH O
Ph Me 43%, dr = 87:13
Relativistic Effects for Platinum and Gold
-
High velocity of electrons , contraction of the 6s orbital and expansion of 5d orbitals
-
High electronegativity, difficult oxidation [Au]
-
Low lying LUMO resulting in higher Lewis acidity [Au]
-
[Au]
Little back donation to π* orbitals but stabilization of carbocations
Leyva-Perez, A.; Corma, A. Angew. Chem. Int. Ed. 2012, 51, 614-635. Gorin, D. J.; Toste, D. F. Nature 2007, 446, 395-403.
[Au]
Cycloisomerization of Enynes Catalyzed by PtCl2 E
PtCl2 (5 mol %)
E
E
toluene, 80°C
E 86%
E = CO2Me Chatani, N.; Morimoto, T.; Muto, T.; Murai, S. J. Am. Chem. Soc. 1994, 116, 6049-6050.
Ts N
Ts
NH N N
PtCl2 79%
O
O
HN
MeO
For milestones, see:
Streptorubine B
Fürstner, A. et al J. Am. Chem. Soc. 2001, 123, 11863. Echavarren, A. M. et al J. Am. Chem. Soc. 2001, 123, 10511. Asymmetric version: Michelet, V.; Gladiali, S.; Genêt, J.-P. et al. Chem. Commun. 2004, 850. Reviews: Fürstner, A.; Davies, P. W. Angew. Chem. 2007, 46, 3410. Fensterbank, L.; Goddard, J.-P.; Malacria M. Comprehensive Organometallic Chemistry, 2007, Vol. 10, 299-368. Hashmi, A. S. K.. Chem. Rev. 2007, 107, 3180. Gorin, D. J.; Toste, D. F. Nature 2007, 446, 395-403. Michelet, V.; Toullec, P. Y.; Genêt, J.-P. Angew. Chem. Int. Ed. 2008, 47, 4268.
Cycloisomerization of Dienynes Catalyzed by PtCl2 OX
OX
OX
H
PtCl2 (5 mol %)
+
Tol., 80°C, 2-9 h
H
X=H
7%
48 %
X = SiMe2CH2Br
5%
61 %
X = Me
_
73 %
4 new C-C bonds 4 new stereogenic centers
See also: Murai, S. et al. J. Am. Chem. Soc. 1998, 120, 9104. For reviews, see: Bruneau, C. Angew. Chem. Int. Ed. 2005, 44, 2328; Echavarren, A. et al. Chem. Comm. 2007, 333.
Behavior of O-Acyl Precursors OX
PtCl2 (5 mol %)
+
Tol., 80°C, 2-9 h
X = COCH3
X = p-COC6H4NO2
OX
XO
88%
3%
76%
4%
H K2CO3 OAc
MeOH
Angew. Chem. Int. Ed. 2002, 41, 2132.
O
93%
Mechanism Proposal for X = H, Me, SiR3 OX
XO PtCl2 X = H, Me, SiMe2CH2Br
OX
OX
OX
OX
H +
PtCl2
OX
PtCl2
OX
PtCl2
H OX
H H
PtCl2
PtCl2
Echavarren, A. M. et al. J. Am. Chem. Soc. 2001, 123, 10511. Inoue, Y. et al. Organometallics 2001, 20, 3704.
H
OX H
Mechanism with Ac, p-COC6H4NO2 Groups (Ohloff-Rautenstrauch Rearrangement)
O
X
O
X O
O
OCOX PtCl2
Cl2Pt
Cl2Pt
E
X = Me, p-C6H4NO2
X
O Cl2Pt
Z
O
Strickler, H.; Davis, J. B.; Ohloff, G. Helv. Chim. Acta 1976, 59, 1328 Rautenstrauch, V. J. Org. Chem. 1984, 49, 950. Review: Marion, N.; Nolan, S. P. Angew. Chem. Int. Ed. 2007, 46, 2750.
OCOX
XOCO
Synthesis of Tricyclic Derivatives AcO
OAc PtCl2 (5 mol %)
88%, 1 dias.
H
Tol., 80°C
AcO
OAc
H
98%, 1 dias.
AcO
OAc
78%, 1 dias.
H
AcO
OAc
63%, 1 dias.
neat, rt
H Adv. Synth. & Cat. 2008, 350, 43 ; J. Organomet. Chem. 2009, 694, 561-565..
Other Applications NO2 O
1. 5 mol% PtCl2
O
O
2. 2N NaOH, rt
Sabina ketone, 83% J. Am. Chem. Soc. 2004, 126, 8656. See also Fürstner et al. ibid 8654.
1. PtCl2, toluene, rt
O p-O2N-Ph-COCl Et3N, 4-DMAP CH2Cl2, rt
HO
2. K2CO3, MeOH, rt
O O2N
77 %
48 % (2 steps)
PtCl2, toluene, rt
MeI, NaH, THF
Org. Lett. 2004, 6, 3771.
O
O
O 54 %
via :
[Pt] O
55 %
Allene Activation [M]
[M]
[M]
•
Nu
R H
Nu
E
Nu
M
• R'
PPh3AuCl (2% mol) AgSbF6 (2% mol) CH2Cl2
[M]
[M]
E
M
M
H R
H
H R R'
Toste D. Angew. Chem. Int. Ed. 2007, 46, 912-914. With PtCl2 Iwasawa, N. Angew. Chem. Int. Ed. 2007, 46, 909.
R R'
R'
Polyquinanes Synthesis
R2
•
R2
R2 R1
OAc
R1
AuClPPh3 / AgSbF6 (2 mol %) CH2Cl2, rt, 10 min
PPh3AuCl (2 %) AgSbF6 (2 %) CH2Cl2, rt 10 min
• AcO
R2
62-80%
[Au] AcO
[Au]
AcO
97 %
Org. Lett. 2007, 9, 2207-09.
Synthesis of Capnellene OTBS HH O
[Au] (2% mol)
O TBSO
OAc
CH2Cl2, 0°C 2h
OAc
(2 dias ~ 50/50)
67 % (5 steps)
85 % (2 steps)
O
OTBS HH
HH
H
Me
62 % (4 steps)
PtO2 (0,3 eq) H2 (1 bar)
OTBS H H
H OH
Me
93 %
OTBS HH
NaBH4 MeOH
AcOH
K2CO3 MeOH
H
H
O
OH
major dias.
(2 dias ~ 50/50)
HH
H
[Au]:
Capnellene Me
Grubbs, R. H. and coll. J. Org. Chem. 1990, 55,843.
Isolated from capnella imbricata
SbF6
Au P t-Bu t-Bu
J. Am.Chem. Soc. 2009, 131, 2993-3006.
Chiral Anion Strategy in Organometallic Catalysis
Ligand
Au
Substrate
Counter-ion
*
For a review on asymmetric gold catalysis, see: Bongers, N.; Krause, N. Angew. Chem. Int. Ed. 2008, 47, 2178
For a recent review on ion pair catalysis, see: J. Lacour, D. Moraleda, Chem. Comm. 2009, 45, 7073 See also: D. Zuccaccia, L. Belpassi, F. Tarantelli, A. Macchioni, J. Am. Chem. Soc. 2009, 131, 3170
Chiral Anion Strategy in Organometallic Catalysis
O O
OAg P O (5 mol %)
NHSO2Mes 5 mol% Ph(Me)2PAuCl
•
SO2Mes N H
benzene, rt
97% yield, 96% ee
Hamilton, G. L.; Kang, E. J.; Mba, M.; Toste, D. Science 2007, 317, 496 R. L. LaLonde, Z. J. Wang, M. Mba, A. D. Lackner, F. D. Toste, Angew. Chem. Int. Ed. 2010, 49, 598 Highlighted in Science: Lacour, J.; Linder, D. Science 2007, 317, 462
Ion Pair Formation
iPr
iPr
iPr O
P O + Cl Au P OAg O iPr
iPr
iPr
31P
CD2Cl2
O O
O P
Au
P
O
! (P-Au) = 33 ppm 31P
! (P-Au) = 27 ppm
Gold-Catalyzed Cycloisomerizations Ph Me R
TsN
Ph
PPh3AuCl (5 mol%) I (5 mol%) X
CH2Cl2, rt or ! C6H6, rt or !
TsN
No catalysis Starting material recovered
O O
OAg P R
O I
OAc dppm(AuCl)2 (2.5 mol%) I (5 mol%)
Ph
benzene/MeOH, 9/1 rt then ! , 55% PhO2S
PhO2S PhO2S
PhO2S PPh3AuCl (5 mol%) I (5 mol%)
CH2Cl2/MeOH, 9/1 7d, rt, 98%
OMe ee = 0%
See also: Echavarren, A. M. et al. Chem. Commun. 2012, 48, 52 ; Nguyen, B. N. Organometallics 2012 in press
From Gold- to Iridium-Catalyzed Cycloisomerizations Vaska s Complex
O O L1
O
O
P
?
O M
AEG
L1
L1
L2
N
O
L2
Ar
Cl PPh3 (20 mol%) Ir Ph3P CO AgX (24 mol%)
H Me
DME, 60 °C 55% - 84%
O
P O
M
L1
AEG
N
Ar Me
Shibata,T.; Kobayashi, Y.; Maekawa, S.; Toshida, N.; Takagi, K. Tetrahedron, 2005, 61, 9018
Optimization of the Conditions Ts
N
Ph IrCl(CO)(PPh3)2 (20 mol%) I (24 mol%)
Ts
Ph
N
solvent, 0.067M, T °C, 23 h Me sealed tube
Me
entry
solvent
T °C
yield
ee
1
DME
90 °C
20%
60%
2
CH3CN
90 °C
-
-
3
1,4-dioxane
100 °C
24%
66%
4
(CH2Cl)2
90 °C
28%
44%
5
benzene
80 °C
40%
73%
6
toluene
110 °C
80%
80%
O O
T °C
c
x
1
70 °C
0.067M
20 mol%
71 h unreproductible results
2
90 °C
0.067M
20 mol%
23 h
83%
82%
3
130 °C
0.067M
20 mol%
23 h
71%
76%
4
90 °C
0.01M
20 mol%
23 h
40%
79%
5
90 °C
0.134M
10 mol%
23 h
80%
81%
6
90 °C
0.250M
5 mol%
23 h
74%
80%
yield
P O
I
entry
t
OAg
ee
Chem. Eur. J. 2011, 17, 13789
Screening of the Catalyst Ts
[M] (20 mol%) Ag-salt (24 mol%)
Ph
N
Me
entry
2
3
Ir Cl(CO)(PPh3)2 Ph2 P Ir P Ph2 Ph3P Rh OC Ir
4
N
toluene, 0.067M, 90 °C, 23 h
[M]
1
Ts
+
Br CO Cl PPh3
Cl Ir Cl PPh2
Ph
Me
Ag-salt
yield
ee
I (R = TRIP)
82%
83%
I (R = TRIP)
10%
43%
I (R = TRIP)
69%
48%
I (R = TRIP)
25%
64%
I (R = TRIP)
51%
52%
+ CO atm.
PPh2
5
Ir
Cl Ir Cl
+ PPh3 + CO atm.
6
IrCl(CO)(PPh3) 2
II (R = 4-tBu)
83%
47%
7
IrCl(CO)(PPh3) 2
III (R = 3,5-CF3)
32%
37%
8
IrCl(CO)(PPh3) 2
IV (R = anthracenyl) 74%
85%
Screening of the Substrates ArO2S
R1
N
R2 R3
O
S
PPh3 Cl Ir (10 mol%) Ph3P CO
O
Me
Me O
Me ! = 80%, ee = 81% O O S N
O2N
Me
Ts
N
O
Ph
Me ! = 16%, ee nd
S
Ph
N
Me
S
O
Ph
N
Me Me ! = 77%, ee = 93% O Ph O N Me ! = 38%, ee = 80%
Cl
N
Me ! = 79%, ee = 89%
Me ! = 76%, ee = 86%
Me O
O
Me ! = 73%, ee = 72% Ts
Ts
R2 R3
Me ! = 74%, ee = 87% NO2 O O Ph S N
Ph
! = 79%, ee = 82% OMe
R1
N
toluene, 0.134M, 90 °C, 23 h
Ph
N
ArO2S
I (12 mol%)
N
Me Me
! = 61%, ee = 86%
O
Ts
H N
Ts Ph
PMP ! = 73%, ee = 88%
N
Me
Me
Me
! = 47%, ee = 43%
Me
! = 16%, ee = 17%
E Ph
H
Ph
E Me ! = 0%, ee -
Conclusion! Ts N
O
AcO
N NHNos H HO
OMe
M
H
O
R
N
R
H
Ph
Highly stimulating mechanistic issues !
Endless pleasure !
N N
N Ph BH3
Playing with heteroatoms for new radical processes...
N N
Si O
F
F
O
Si
NC
R
F B
O S
O S
Un travail dʼéquipe…! COS team Dr. Muriel Amatore Dr. Corinne Aubert Dr. Marion Barbazanges Dr. Etienne Derat Dr. Marine Desage - El Murr Dr. Anne-Lise Dhimane Dr. Jean-Philippe Goddard Prof. Max Malacria Dr. Virginie Mouriès-Mansuy Dr. Cyril Ollivier Dr. Marc Petit
Cascade team
Asymmetric team
Christophe Blaszykowski Yohan Contie Julien Coulomb Priscille Devin Audrey Ekomié Alexandre Gross Marie-Hélène Larraufie Emily Mainetti Malika Makhlouf Brahmi Dr. Geoffroy Sorin Dr. Shau-Hua Ueng
Franck Brebion Dr. Victor Certal Hugo Lenormand Rocio Martinez-Mallorquin Dr. Francisco Najera Dr. Kai Song Dr. Guillaume Vincent Maxime Vitale Dr. Qi Wu
Prof. Christine Courillon, U. Paris-Diderot Dr. Emmanuel Lacôte, C2P2 Lyon Prof. Vincent Gandon, ICMMO U. Paris Sud Dr. Serge Thorimbert, IPCM, UPMC
Golden team Mylène Augé Erica Benedetti Matthieu Bernard Nicolas Cadran Kevin Cariou Nicolas das Neves Lisa Diab Pierre Garcia Dr. Gwenaëlle Hervé Dr. Yousseh Harrak Dr. Alexandra Hours Dr. Florian Jaroschik Gilles Lemière Nicolas Marion Dr. Xavier Moreau Antoine Simonneau Dr. Tran Anh Tuan Dr. Riadh Zriba
Prof Jean-Claude Tabet, Dr. Denis Lesage, IPCM, UPMC Dr. Yves Gimbert, UJF - Grenoble Dr. Hani Amouri, IPCM, UPMC Prof. Lahouari Krim, Dr. Emilie-Laure Zins, LADIR UPMC Dr. François Stoffelbach, Dr. Jutta Rieger, LCP UPMC Prof. Ilan Marek, Technion Haifa Prof. Dennis Curran, U. Pittsburgh, Profs. Ilhyong Ryu & Takahide Fukuyama, Osaka Prefecture University
"Radicaux Verts"
"Allenes"
"Credox"
"Sacaor"
