View
3
Download
0
Category
Preview:
Citation preview
Vincent Gandon
Institut de Chimie Moléculaire et des Matériaux d’Orsay, UMR 8182 Université Paris-sud
Sélectivité en catalyse moléculaire :
Assistance de la chimie théorique
IIIème Journée de Simulation Numérique en Chimie à Paris-S ud
12 novembre 2014
2
Thermal (Berthelot, 1866)
Catalytic (Reppe, 1948)
Catalytic (Vollhardt, 1970)
Metal-Catalyzed [2+2+2] Cycloaddition of Alkynes
Stoichiometric (Vollhardt, 1970)
CpCo(CO)
CoCp(CO)
CoCp
CpCo
CpCo
Co
CpCo
CpCo
CO
CO
Co
OC CO
Cp
3
Cobalt-Catalyzed [2+2+2] Cyclotrimerization of Alkynes
CpCo(CO)
CoCp(CO)
CoCp
CpCo
CpCo
Co
CpCo
CpCo
CO
CO
Co
OC CO
Cp
4
Cobalt-Catalyzed [2+2+2] Cyclotrimerization of Alkynes
Albright, T. A. J. Am. Chem. Soc. 1999, 121, 6055Koga, N. Bull. Chem. Soc. Jpn. 2005, 78, 781
5
B3LYP/6-311+G(2d,2p)
∆E (kcal/mol)
Metal-Assisted [4+2] Cycloaddition
J. Am. Chem. Soc. 2007, 129, 8860
PPh3 C2H4 THF
6J. Am. Chem. Soc. 2007, 129, 8860
Unassisted [4+2] Cycloaddition
PH3 PMe3 CO
0.0
Co
L
CpEE
CpCoL +
E
E
CpCo
L
+E E
CpCo
L
EE
(E = CO2H)
+18.0
29.8
29.2
90.8
B3LYP/6-311+G(2d,2p)
∆E (kcal/mol)
7Chem. Eur. J. 2007, 13, 7466
∆H298 (kcal/mol)
B3LYP/6-311+G(2d,2p)
Tethered Systems
8Chem. Eur. J. 2007, 13, 7466
∆H298 (kcal/mol)
B3LYP/6-311+G(2d,2p)
Tethered Systems
9Chem. Eur. J. 2007, 13, 7466
Tethered Systems
Cycloisomerization of enynes: Pt(II)
P
Pt(PhCN)2, (BF4)2
P
Ph Ph
Ph Ph 1
[Pt] (10 mol%)
CHCl3, rt, 20 h
[Pt] = PtCl2, 83%[Pt] = 1, 92%
2 3
MeO
MeO
MeO
MeO
B3LYP/LANL2DZ(Pt)/6-31G(d,p)
Cycloisomerization of enynes: Pt(II)
Cycloisomerization of enynes: Pt(II)
B3LYP/LANL2DZ(Pt)/6-31G(d,p)
Electrospray ionization tandem mass spectrometric experiments.Consecutive CAR/CID sequences (Collision-Activated Reaction, Collision-Induced Dissociation)
Mass spectroscopy (CAR/CID)
Cycloisomerization of enynes: Pt(II)
Mass spectroscopy (CAR/CID)
Cycloisomerization of enynes: Pt(II)
Cycloisomerization of enynes: Pt(II)
ChemCatChem 2009, 1, 138Chem. Sci. 2011, 2, 2417
16
Chatani, Org. Lett. 2006, 8, 2155
Cycloisomerization of enynes
17
Yu, A. J. Org. Chem. 2014, 3, 842Yu, J. Org. Chem. 2014, 79, 3809Yu, J. Org. Chem. 2012, 77, 8527
B3LYP/LANL2DZ(Ga)/6-31G(d)
Cycloisomerization of enynes
18
Yu, A. J. Org. Chem. 2014, 3, 842Yu, J. Org. Chem. 2014, 79, 3809Yu, J. Org. Chem. 2012, 77, 8527
B3LYP/LANL2DZ(Ga)/6-31G(d)
Cycloisomerization of enynes
∆G298 (kcal/mol)
V1
Diapositive 18
V1 le trans nonconj est écrit cis dans le papier !Vincent; 10/11/2014
19
Cycloisomerization of enynes
Yu, A. J. Org. Chem. 2014, 3, 842Yu, J. Org. Chem. 2014, 79, 3809Yu, J. Org. Chem. 2012, 77, 8527
B3LYP/LANL2DZ(Ga)/6-31G(d)
GaCl2
H
H
GaCl2
H
H
H
G = 12.4 kcal/mol
G = 9.2 kcal/mol
+
H
GaCl2
+
∆G298 (kcal/mol)
20
B3LYP/LANL2DZ(Ga)/6-31G(d)
Cycloisomerization of enynes
Cationic Gallium(III) Complexes
Ga-F(1) 1.920(4) ÅSb-F(1) 1.987(1) ÅSb-F(2,3,4,5,6)av 1.87 Å
Inorg. Chem. 2013, 52, 11493Inorg. Chem. 2013, 52, 506Organometallics 2014, 33, 594
Cycloisomerization of enynes
Cycloisomerization of enynes
B3LYP/6-31G(d)
∆G298 (kcal/mol)
Cycloisomerization of enynes
25
B3LYP/6-31G(d)
Cycloisomerization of enynes
∆G298 (kcal/mol)
26
Cycloisomerization of enynes
B3LYP/6-31G(d)
∆G298 (kcal/mol)
Cycloisomerization of enynes
B3LYP/6-31G(d)
GaCl2L
H
H
LCl2Ga H
H
H
GaCl2L
H
G = ?
+
+
G = ?
E
E
E
E
E
E
(E = CO2Me)
E 7.5 kcal/mol
∆G298 (kcal/mol)
Bogdan Iorga (ICSN)Etienne Derat (P6)Tom Albright (Houston)Jeremy Harvey (Bristol)CRIHAN
Acknowledgements
Cycloisomerization of enynes: Pt(II)
B3LYP/LANL2DZ(Pt)/6-31G(d,p)
Cycloisomerization of enynes: Pt(II)
B3LYP/LANL2DZ(Pt)/6-31G(d,p)
Cycloisomerization of enynes
B3LYP/6-31G(d)
Cycloisomerization of enynes
B3LYP/6-31G(d)
Cycloisomerization of enynes
B3LYP/6-31G(d)
Recommended