Reactions between N-Heterocyclic Carbene and Lutetium-Metallofullerenes: High Regioselectivity Directed by Electronic Effect in Addition to Steric Hindrance.

Author(s) Shen, W.; Yang, L.; Wu, Y.; Bao, L.; Li, Y.; Jin, P.; Fang, H.; Xie, Y.; Lu, X.
Journal J Org Chem
Date Published 2019 Jan 18
Abstract

The Lewis acid-base pairing reaction between strained N-heterocyclic carbene (NHC) and endohedral metallofullerenes (EMFs) is an efficient strategy to obtain stable derivatives in a highly regioselective manner. Herein, we report an in-depth study on the reactions between 3-dimesityl-1 H-imidazol-3-ium-2-ide (1) and three different EMFs, namely, LuN@ I(7)-C, Lu@ C(8)-C, and Lu@ C(9)-C, respectively. Only one monoadduct is obtained for each EMF under certain conditions, demonstrating surprisingly high regioselectivity and exclusive formation of monoadducts. X-ray results of the derivatives of LuN@C reveal that an epoxide adduct (2a) with a specific [6,6,6]-carbon atom of the C cage singly bonded to the normal carbene center (C2) of the NHC is obtained under ambient condition, whereas a pure argon atmosphere gives 2b with an abnormal C5-bonding structure. In contrast, the derivatives of Lu@C (3 and 4) are both normal C2-bonding [5,6,6]-adducts without oxygen addition, even though air is involved in the reaction. Our theoretical results confirm that the remarkably high regioselectivity and the quantitative formation of monoadducts are direct result from the distributions of molecular orbital and electrostatic potential on the cage surfaces in addition to the previously assumed steric hindrance between the fullerene cage and the NHC moiety.

DOI 10.1021/acs.joc.8b02423
ISSN 1520-6904
Citation Shen W, Yang L, Wu Y, Bao L, Li Y, Jin P, et al. Reactions between N-Heterocyclic Carbene and Lutetium-Metallofullerenes: High Regioselectivity Directed by Electronic Effect in Addition to Steric Hindrance. J Org Chem. 2019;84(2):606-612.

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