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Computational chemical analysis of Ru(II)‐Pheox–catalyzed highly enantioselective intramolecular cyclopropanation reactions
Author(s) -
Nakagawa Yoko,
Nakayama Naofumi,
Goto Hitoshi,
Fujisawa Ikuhide,
Chanthamath Soda,
Shibatomi Kazutaka,
Iwasa Seiji
Publication year - 2019
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.23033
Subject(s) - cyclopropanation , intramolecular force , enantioselective synthesis , chemistry , cyclopropane , carbene , catalysis , density functional theory , intramolecular reaction , stereochemistry , computational chemistry , organic chemistry , ring (chemistry)
Computational chemical analysis of Ru(II)‐Pheox–catalyzed highly enantioselective intramolecular cyclopropanation reactions was performed using density functional theory (DFT). In this study, cyclopropane ring–fused γ‐lactones, which are 5.8 kcal/mol more stable than the corresponding minor enantiomer, are obtained as the major product. The results of the calculations suggest that the enantioselectivity of the Ru(II)‐Pheox–catalyzed intramolecular cyclopropanation reaction is affected by the energy differences between the starting structures 5l and 5i . The reaction pathway was found to be a stepwise mechanism that proceeds through the formation of a metallacyclobutane intermediate. This is the first example of a computational chemical analysis of enantioselective control in an intramolecular carbene‐transfer reaction using C 1 ‐symmetric catalysts.