Kulinkovich reaction

The Kulinkovich reaction describes the organic synthesis of cyclopropanols via reaction of esters with dialkyldialkoxytitan reagents, generated in situ from Grignard reagents bearing hydrogen in beta-position and titanium(IV) alkoxides. Reaction was found by Kulinkovich and coworkers in 1989. Titanium reagent could be used catalytically.

Additional recommended knowledge

What is the Sensitivity of my Balance?

How to ensure accurate weighing results every day?

Essential Laboratory Skills Guide

Titanium catalyst: ClTi(OiPr)₃ or Ti(OiPr)₄, ClTi(OtBu)₃ or Ti(OtBu)₄
Grignard reagents: EtMgX, PrMgX, BuMgX.
Solvents: Et₂O, THF, Toluol.
Tolerated Functional Groups: Ethers R-O-R, R-S-R, Imines RN=CHR.
Amides, primary and secondary amines, carbamates are not stable to the reaction condition

Reaction mechanism

References

1. Kulinkovich, O. G.; Sviridov, S. V.; Vasilevskii, D. A.; Pritytskaya, T. S. Zh. Org. Khim. 1989, 25, 2244; Kulinkovich, O.; Sviridov, S.V.; Vasilevski, D.A. Synthesis, 1991, 234.
2. Reviews: a) Kulinkovich, O. G.; de Meijere, A. Chem. Rev. 2000, 100, 2789. (b) Sato, F.; Urabe, H.; Okamoto, S. Chem. Rev. 2000, 100, 2835. c) Kulinkovich, O. G. Russ. Chem. Bull. No. 5, , 2004,1022—1043.
3. Mechanism: Wu, Y.-D.; Yu, Z.-X. J. Am. Chem Soc. 2001, 123, 5777.
doi:ja010114q

See also