vincent gandon institut de chimie moléculaire et des matériaux dorsay, umr 8182 université...
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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
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