Global InformationKulinkovich reaction information
 | This article relies excessively on references to primary sources. (February 2023) |
| Kulinkovich reaction | |
|---|---|
| Named after | Oleg Kulinkovich |
| Reaction type | Ring forming reaction |
| Identifiers | |
| Organic Chemistry Portal | kulinkovich-reaction |
| RSC ontology ID | RXNO:0000682 |
The Kulinkovich reaction describes the organic synthesis of substituted cyclopropanols through reaction of esters with dialkyldialkoxytitanium reagents, which are generated in situ from Grignard reagents containing a hydrogen in beta-position and titanium(IV) alkoxides such as titanium isopropoxide.[1] This reaction was first reported by Oleg Kulinkovich and coworkers in 1989.[2]
Titanium catalysts are ClTi(OiPr)3 or Ti(OiPr)4, ClTi(OtBu)3 or Ti(OtBu)4, Grignard reagents are EtMgX, PrMgX or BuMgX. Solvents can be Et2O, THF, toluene. Tolerated Functional Groups: Ethers R–O–R, R–S–R, Imines RN=CHR. Amides, primary and secondary amines. Carbamates typically do not tolerate the reaction conditions, but tert-butyl carbamates (N-Boc derivatives) survive the transformation.
An asymmetric version of this reaction is also known with a TADDOL-based catalyst.[1]
- ^ a b Cha, Jin Kun; Kulinkovich, Oleg G. (2012). "The Kulinkovich cyclopropanation of carboxylic acid derivatives". Organic Reactions. 77: 1–159. doi:10.1002/0471264180.or077.01. ISBN 978-0471264187.
- ^ Kulinkovich, O. G.; Sviridov, S. V.; Vasilevskii, D. A.; Pritytskaya, T. S. (1989). "Reaction of ethylmagnesium bromide with carboxylic acid esters in the presence of tetraisopropoxytitanium". Zh. Org. Khim. 25: 2244.