Abstract
<jats:title>Abstract</jats:title> <jats:p>This chapter describes intra‐ and intermolecular kulinkovich cyclopropanation reactions of carboxylic esters with olefins – bicyclo[3.1.0]hexan‐1‐ol and trans‐2‐benzyl‐1‐methylcyclopropan‐1‐ol. The low‐valent titanium‐mediated cyclopropanation of esters provides easy access to 1,2‐cis‐alkylcyclopropanols, complementing the venerable Simmons‐Smith cyclopropanation of silylenol ethers or derivatives. Satisfactory levels of diastereoselective cyclopropanation reactions are possible by employing 1‐alkenes having a suitable adjacent stereocenter6 or secondary homoallylic alcohols. Styrenes and vinylsilanes also undergo coupling with allylic alcohols in the presence of the cyclopentyl Grignard reagent under the typical Kulinkovich reaction conditions. The cyclopropanol substrates are readily available by the Kulinkovich cyclopropanation of the corresponding lactones. The chapter focuses on regioselective ring opening of cyclopropanols at the unsubstituted carbon. The alternative mode of ring opening relies on generation of beta‐keto alkyl radical intermediates. In conclusion, the Kulinkovich cyclopropanation reaction provides ready access to attractively functionalized cyclopropanols.</jats:p>