Organic chemists have always been fascinated by the cyclopropane subunit.1 The smallest cycloalkane is found as a basic structural element in a wide range of naturally occurring compounds.2 Moreover, many cyclopropane-containing unnatural products have been prepared to test the bonding features of this class of highly strained cycloalkanes3 and to study enzyme mechanism or inhibition.4 Cyclopropanes have also been used as versatile synthetic intermediates in the synthesis of more functionalized cycloalkanes5,6 and acyclic compounds.7 In recent years, most of the synthetic efforts have focused on the enantioselective synthesis of cyclopropanes.8 This has remained a challenge ever since it was found that the members of the pyrethroid class of compounds were effective insecticides.9 New and more efficient methods for the preparation of these entities in enantiomerically pure form are still evolving, and this review will focus mainly on the new methods that have appeared in the literature since 1989. It will elaborate on only three types of stereoselective cyclopropanation reactions from olefins: the halomethylmetal-mediated cyclopropanation reactions (eq 1), the transition metal-catalyzed decomposition of diazo compounds (eq 2), and the nucleophilic addition-ring closure sequence (eqs 3 and 4). These three processes will be examined in the context of diastereoand enantiocontrol. In the last section of the review, other methods commonly used to make chiral, nonracemic cyclopropanes will be briefly outlined.

Stereoselective Cyclopropanation Reactions

Synthesis of cyclopropane containing natural products

Recent advances in the preparation and synthetic applications of oxiranes

Tetrahedron report number 195 (R)- and (S)-2,3-0-isopropylideneglyceraldehyde in stereoselective organic synthesis

The development of efficient methods for the facile construction of important molecular architectures is a central goal in organic synthesis. An unprecedented organocatalytic asymmetric cascade Michael-alkylation reaction of α,β-unsaturated aldehydes with bromomalonates has been developed. The process, efficiently catalyzed by chiral diphenylprolinol TMS ether in the presence of base 2,6-lutidine, serves as a powerful approach to the preparation of synthetically and biologically important cyclopropanes in high levels of enantio- and diastereoselectivities. Remarkably, the power of the cascade process is fueled by its high efficiency of the production of two new C−C bonds, two new stereogenic centers, and one quaternary carbon center in one single operation, which otherwise is difficult to achieve by traditional strategies. Moreover, the beauty of the cascade process is further underscored by the nature of the product formation depending on the reaction conditions. With the alternation of base from 2,6-lut...

Organocatalytic Enantioselective Cascade Michael-Alkylation Reactions: Synthesis of Chiral Cyclopropanes and Investigation of Unexpected Organocatalyzed Stereoselective Ring Opening of Cyclopropanes

Synthesis of r epi chlorohydrin and s epi chlorohydrin

Synthesis of (R)- and (S)-epichlorohydrin

Mode of nucleophilic addition to epichlorohydrin and related species: chiral aryloxymethyloxiranes

Synthesis of 4-substituted 2h-naphth(1,2-b)-1,4-oxazines, a new class of dopamine agonists

ANTIHYPERTENSIVE β-ADRENERGIC BLOCKING AGENTS: N-ARALKYL ANALOGS OF 2-(3-(TERT-BUTYLAMINO)-2-HYDROXYPROPOXY)-3-CYANOPYRIDINE

D. E. Mcclure

Papers

Synthesis of r epi chlorohydrin and s epi chlorohydrin

Synthesis of (R)- and (S)-epichlorohydrin

Mode of nucleophilic addition to epichlorohydrin and related species: chiral aryloxymethyloxiranes

Synthesis of 4-substituted 2h-naphth(1,2-b)-1,4-oxazines, a new class of dopamine agonists

ANTIHYPERTENSIVE β-ADRENERGIC BLOCKING AGENTS: N-ARALKYL ANALOGS OF 2-(3-(TERT-BUTYLAMINO)-2-HYDROXYPROPOXY)-3-CYANOPYRIDINE