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.

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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