Enantioselective palladium-catalyzed hydrosilylation of styrene: Influence of electronic and steric effects on enantioselectivity and catalyst design via hybrid QM/MM molecular dynamics simulations

Organometallics

Volumn 25, Issue 5, 2006, Pages 1151-1157

  Magistrato, Alessandra ^a   Togni, Antonio ^b   Rothlisberger, Ursula ^c  

^a DEMOCRITOS NATIONAL SIMULATION CENTER   (Italy)

^b ETH ZURICH   (Switzerland)

^c EPFL   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CATALYSTS; COMPUTER SIMULATION; ISOMERS; MOLECULAR DYNAMICS; PALLADIUM; THERMODYNAMIC STABILITY;

CHARGE DISTRIBUTION; MOLECULAR DYNAMICS SIMULATIONS; STEREOSELECTIVITY; STERIC EFFECTS;

STYRENE;

EID: 33644990899     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om050246i     Document Type: Article

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64. 33b
65. The calculation of the Mulliken charge distribution of the free benzylic radical was performed using the ADF 2.3 package. The charge analysis has been performed with a double-ξ basis without polarization functions for all atoms.
66. An analysis of the electronic structure shows the presence of an electronic correlation between the allylic system and the diphenylphosphine ligand. See Figure SI in the Supporting Information.
67. From the computational point of view, in addition to the presence of strong steric contacts, the importance of steric effects is suggested by the lack of a clear correlation in the charge distribution of the allylic isomers. From the experimental point of view, the observed 67.2% ee using 4-(trifluoromethyl)styrene as substrate does not correlate with the high electron-withdrawing nature of the para substituent (Table 1 and ref 6) and may be caused by the steric hindrance of the para substituent.
68. Here, the methyl group is used as a simple prototype substituent to increase the steric bulk of the mesityl group very directionally. However, we should point out that isomers with the ethyl rotated by 180° are likely to be thermodynamically favored over the calculated conformer. In addition, we should point out that this is the simplest possible modification that we can do to the catalyst to increase its steric hindrance in a very specific manner. From an experimental point of view it is very unlikely this catalyst could be operative.