1989年，O.G. Kulinkovich报道了在一倍当量的四异丙氧钛存在下简单羧酸酯和过量的乙基溴化镁作用得到1-烷基环丙醇的反应。此反应在催化量的Ti(Oi-Pr)4存在下，两倍当量的格氏试剂也可进行。
在钛(II)催化下，羧酸酯或酰胺和格氏试剂反应一锅法得到相应的1-烷基环丙醇或1-烷基环丙胺的反应被称为Kulinkovich反应。
反应机理
首先Ti(Oi-Pr)4先和两倍当量的乙基溴化镁反应得到二烷基化产物，二乙基钛中间体迅速进行β-H消除，得到钛杂环丙烷中间体，作为1,2-二碳负离子等价物和羰基反应，进行二烷基化。另外的乙基溴化镁加成到钛上，引发第一次碳碳键形成得到氧钛在环戊烷络合物。开始底物酯的烷氧基以镁盐的形式离去（酰胺则是氧化镁盐消除），第二次碳碳键形成得到环丙烷环。生成的环丙氧钛与格氏试剂反应进行烷基化，则二乙基钛中间体再生，产物的镁盐生成。酸化得到产物。
反应实例
【Org. Lett. 2001, 3, 3273-3275】
【Org. Lett. 1999, 1, 1799-1801】
【J. Am. Chem. Soc. 2001, 123, 11322-11324】
【J. Am. Chem. Soc. 1995, 117, 9919-9920】
A 50-mL round-bottomed flask containing an oversize cylindrical magnetic stirring bar was charged with 678 mg neat methyl thiomethyl ether (1.53 mmol). The flask was evacuated and purged with nitrogen three times to degas the substrate. In a glove bag, a preweighed portion of Ti(O-i-Pr)3Cl (997 mg, 3.83 mmol, 2.5 eq.) was added directly to the flask as a solid. The contents of the flask were then dissolved in 5.5 mL THF, and the resulting colorless solution was cooled to 0◦C. Freshly prepared 1.64 M EtMgBr in THF (4.66 mL, 7.64 mmol, 5.0 eq.) was added dropwise to the flask from a syringe over 5 min. The addition initially caused a dark orange and ultimately a brown-black discoloration of the reaction mixture. After gas evolution (ethane) had subsided, the ice bath was removed, and the mixture was warmed to room temperature. The flask was then sealed tightly with a plastic cap, and the thick, dark brown mixture was stirred vigorously at room temperature for 48 h. After diluting with 10 mL Et2O, the contents of the flask were then poured into a separatory funnel containing 125 mL saturated ammonium chloride. The aqueous layer
was then extracted with Et2O (4 × 100 mL). The combined organic washes were dried over MgSO4 and filtered to a colorless solution. Concentration and purification over silica gel (Rf = 0.30 in 4.5:1 hexanes/ EtOAc) afforded 404 mg cyclopropanyl alcohol as a colorless
oil, in a yield of 60%.
【J. Am. Chem. Soc., 2005, 127, 13813】
To a solution of 150 g ethyl 2-{[tert-butyl(diphenyl)silyl]-oxy}acetate (0.46 mol) in 3.0 L THF was added 30 mL Ti(O-i-Pr)4 (0.10 mol) at −10◦C. A solution of 365 mL 3.0 M EtMgBr in THF (1.09 mol) was added to the mixture dropwise within 4 h under nitrogen, while temperature was controlled < 5◦C. The mixture was allowed to warm to 25◦C and stirred for an additional h. The reaction mixture was quenched by adding 400 mL water dropwise for 1 h below 10◦C. After removal of THF, the aqueous layer was extracted with n-hexane (3 × 500 mL), and the combined extracts were washed with 300 mL brine and 300 mL water. The organic layer was concentrated in vacuo, and the residue was diluted with 150 mL n-heptane. The solution was slowly stirred to generate white solids at −5◦C, and the solids were collected to afford 84.0 g 1-({[tert-butyl(diphenyl)silyl]oxy}methyl)cyclopropanol. The second crop of
1-({[tert-butyl(diphenyl)silyl]oxy}methyl)cyclopropanol (30 g) was obtained from the mother liquor. A total of 114 g cyclopropanol was obtained, in a yield of 80%.
【J. Med. Chem., 2004, 47, 2864】
参考资料：
一、Strategic Applications of Named Reactions in OrganicSynthesis, László Kürti and Barbara Czakó, Kulinkovich Reaction, page 256-257。
二、Comprehensive Organic Name Reactions and Reagents, by Zerong Wang，P1708。
