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Transcript of Vincent Gandon Institut de Chimie Moléculaire et des Matériaux dOrsay, UMR 8182 Université...
Vincent GandonVincent Gandon
Institut de Chimie Moléculaire et des Matériaux d’Orsay, UMR 8182 Institut de Chimie Moléculaire et des Matériaux d’Orsay, UMR 8182 Université Paris-sudUniversité Paris-sud
Mécanismes réctionnels en catalyse homogène :
Assistance de la chimie théorique
Les simulations numériques en chimie à Paris-sud
24 octobre 2012
Asymmetric Carbocyclizations: Chiral Anion Strategy
p-TsN
Me
IrCl(CO)(PPh3)2 (10 mol%)
Toluene, 90 °C23 h, c 0.134M
Ph
silver phosphate (12 mol%) p-TsNPh
Me
83%, 47% ee
O
OP
O
OAg
tBu
tBu
74%, (85% ee)
O
OP
O
OAg
32%, 37% ee
O
OP
O
OAg
CF3
CF3
CF3
CF3
O
OP
O
OAg
iPriPr
iPriPr
iPr
iPr
80%, 81% ee
Asymmetric Carbocyclizations: Chiral Anion Strategy
OO
P
O
O
IrPPh3
Ph3P
OC
Asymmetric Carbocyclizations: Chiral Anion Strategy
TsN PhMe
Toluene, 92 °C,
ClIr
COPh3P
PPh3
(0.02 mmol)
(S)-P* (0.024 mmol)
(0.1 mmol)
(CO 1962 cm-1)
(CO 1966 cm-1)
reaction mixture
sealed tube
(CO 1966 cm-1)
O
OP
O
O
IrPPh3
Ph3P CO
25.6 ppm
14.8 ppm
25.5 ppm
3.4 ppm
25.5 ppm
3.4 ppm
31P NMR
Toluene, rt, 15 h
NTs
Ir
CO
H3P PH3
0.0
6-endo11.54
-17.22
NTs
IrOC
PH3
H3P
-6.12
-37.87NTs
Ir
CO
PH3H3P
1,2-H shif tPh
Ph
Me
Me
MePh
Asymmetric Carbocyclizations: Chiral Anion Strategy
DFT, DFT, GG298298 (kcal/mol) (kcal/mol)B3LYP/LANL2DZ/6-31G**
Asymmetric Carbocyclizations: Chiral Anion Strategy
NTsPhMe
+ [Ir(CO)(PH3)2]+OO
POO
NTs
Ph
MeNTs
Ph
Me
Chem. Eur. J. 2011, 17, 13789
Cyclization of Diynyl Esters
O
Ph
O
O Ph
OSiO2
PhO
O Ph3PAuClAgSbF6
OCOR
•
OR'
R'
OR
O
R'
R
O
Au+
Au+5-exo
Au
O
R'
R O
AuH
O
O
Au
H3P
•
Au
PH3
O
Au
PH3
O
O
H
OH3P
(0.0)
+1.0
(-28.2) (-29.5) (-57.8)
+5.4O
O
+7.8
ACIE 2011, 6868
DFT, DFT, HH298298 (kcal/mol) (kcal/mol)B3LYP/LANL2DZ/6-31G**
Cyclization of Diynyl Esters
Au+
+
Ph
O
CD3
O
+
O O
t-Bu
O O
O
Ph
O
D3C
O
t-Bu
O O
O
H3C
Cyclization of Diynyl Esters
92%
AuClPPh3 (2 mol%)AgSbF6 (2 mol%)
CH2Cl2, rt, 10 min
AcO
H
AcO
H
OR2
OR2
HHR1 = H, R2 = Ac, 98%R1 = Me, R2 = PNB, 96%
92%
R1
R1
R1
R1
OAc
OAc
OL 2007, 2207
1-Allene Gold Complexes
Linear Triquinanes: Synthesis of 9(12)-Capnellene
JACS 2009, 2993
TBSO OAc
TBSOH H
OAc
CH2Cl2, 0 °C2 h 85% (2 steps)
TBSOH H
OH
K2CO3(20 mol%)
MeOH
Au PtBu
tBu
SbF6
(2 mol%)
MeCN
-+
LiAlH4,THF, 0 °C
H H
H
BuLiPh3PMeBr
capnellene, 77%
TBSOH H
H
OH H
H81% (2 steps)
1- PtO2, H22- NaH, CS2, MeI3- Bu3SnH, AIBN
59% (3 steps)
1- TBAF2- Dess-Martin
TBSOH H
OHH
85%
•AcO
H
Au+
AcOH
Au
AcOO
HO
+Au
O O O
Au
O
Au+
Au+
1-Allene Gold Complexes
Au
+H
Me
H
MeAu
H
Me
H
Me
AuBr3
0.0 1.4
+
DFT, DFT, HH298298 (kcal/mol) (kcal/mol)B3LYP/LANL2DZ/6-31G**
1-Allene Gold Complexes
Au
+H
Me
Me
MeAu
H
Me
Me
Me
AuBr3
10.0 0.0
+
DFT, DFT, HH298298 (kcal/mol) (kcal/mol)B3LYP/LANL2DZ/6-31G**
1-Allene Gold Complexes
Chirality Transfers
ACIE 2008, 7534
AuCl(PPh3) (2 mol%)AgSbF6 (2 mol%)
CH2Cl2, 20 °C, 2 hOAc
OAc
92% ee 90% ee
• 1-5 mol% [(Ph3PAu)3O]BF4
CHCl3, 60 °C
exo-Cyclizations
•
AuL+
AuL+
•
LAu
•
AuL
LAuLAu
HAuL
H
H+
+ H+
AuLH
AuL+
- AuL+
LAu
LAu+
ACIE 2006, 7596
Toste, Houk JACS 2008, 4517• 1-5 mol% [(Ph3PAu)3O]BF4
CHCl3, 60 °C
exo-Cyclizations
•
AuL+
AuL+
•
LAu
•
AuL
LAuLAu
HAuL
H
H+
+ H+
AuLH
AuL+
- AuL+
LAu
LAu+
Polynuclear Gold Complexes
+Cat. (2 mol%)
CHCl3
Cat. Conditions % Yield (rat io)
ABC
RT, 1 hreflux, 7 hRT, 1 h
87 (20 : 1)35 (1 : 0)100 (5 : 1)
A: Ph3PAuNTf2 B: (Ph3PAu)3OBF4 C:P AuSbF6
t-But-Bu
MeO
MeO
MeO
MeO
MeO
MeO
1
[1 H + (Ph3PAu)2]+
m/ z 1099
[1 H + ((biph)(t-Bu)2PAu))2]+
m/z 1171
OMeOMe
B
C
(+)
ES
Iin
fus
ion
inC
DC
l 3
A
A: Ph3PAuNTf2B: (Ph3PAu)3OBF4
C:
P Au+ , SbF6-
t-But-Bu
Mass spectroscopy (CAR)Mass spectroscopy (CAR)
Polynuclear Gold Complexes
MeO
MeO
AuPR3
AuPR3
AuPPh31 equiv
Traces70
5 mol%
Ph3PAuNTf2 (mol%)
510
% Yield
RT
MeO MeO
MeOMeO
MeO
MeOPh3PAuNTf2
Intermediacy of Gold Acetylides?
Intermediacy of Gold Acetylides?
AuPPh3+
MeO
MeO
AuPPh3
AuPPh3
AuPPh31 equiv
Traces70
5 mol%
Ph3PAuNTf2 (mol%)
510
% Yield
RT
MeO MeO
MeOMeO
MeO
MeOPh3PAuNTf2
Intermediacy of Gold Acetylides?
Chem. Sci. 2011, 2, 2417
AuPH3 H3PAu
G = 0.0 G = 26.9 G = 20.2 G = 10.3
+ H3PAuOH + H3PAuOH2++ (H3PAu)2OH+ + H2O
H3PAu
AuPH3
AuPH3 H3PAu
G = 0.0 G = 33.0 G = 24.4 G = 35.1
+ H3PAu+
+ H2O+ H3PAu+
+ H3O+
+ 2 H3PAu+
+ H2O+ H3O+
H3PAu
AuPH3
DFT, DFT, GG298298 (kcal/mol) (kcal/mol)B3LYP/LANL2DZ/6-31G**
Facilities
Paris 6 CRIHAN
ICSN
IDA