Methods for the synthesis of donor-acceptor cyclopropanes

Abstract

The interest in cyclopropane derivatives is caused by the facts that, first, the three-carbon ring is present in quite a few natural and biologically active compounds and, second, compounds with this ring are convenient building blocks for the synthesis of diverse molecules (acyclic, alicyclic and heterocyclic). The carbon–carbon bonds in cyclopropane are kinetically rather inert; hence, they need to be activated to be involved in reactions. An efficient way of activation is to introduce vicinal electron-donating and electron-withdrawing substituents into the ring; these substrates are usually referred to as donor-acceptor cyclopropanes. This review gives a systematic account of the key methods for the synthesis of donor-acceptor cyclopropanes. The most important among them are reactions of nucleophilic alkenes with diazo compounds and iodonium ylides and approaches based on reactions of electrophilic alkenes with sulfur ylides (the Corey – Chaykovsky reaction). Among other methods used for this purpose, noteworthy are cycloalkylation of CH-acids, addition of α-halocarbonyl compounds to alkenes, cyclization via 1,3-elimination, reactions of alkenes with halocarbenes followed by reduction, the Simmons – Smith reaction and some other. The scope of applicability and prospects of various methods for the synthesis of donor-acceptor cyclopropanes are discussed. The bibliography includes 530 references.

Three‐Component Gallium(III)‐Promoted Addition of Halide Anions and Acetylenes to Donor–Acceptor Cyclopropanes

“…Donor–acceptor cyclopropanes (DACs), and 2‐aryl cyclopropane‐1,1‐dicarboxylates (ACDCs) 1 in particular, have been known for a long time in organic synthesis as versatile building blocks for the assembly of various carbo‐ and heterocyclic structures, including natural compounds and their analogues . The use of DACs as 1,3‐zwitterions is known best and has been well developed.…”

Four‐Membered Cycle Formation Challenge: GaCl3‐Promoted Formal [2+2]‐Cycloaddition of Donor–Acceptor Cyclopropanes to Bicyclobutylidene

“…Donor–acceptor cyclopropanes ( 1 , DAC), are known for their ability at opening the three‐membered ring in the presence of Lewis acids and in situ generation of 1,3‐zwitterionic, and other related intermediates . The presence of highly reactive carbocationic centers in such intermediates opens rich prospects for reactions with various double and triple carbon–carbon bonds .…”

(3+3)‐Annulation of Donor–Acceptor Cyclopropanes with Diaziridines

“…[1,2] In contrast to alkenes, imines,a lkynes,a nd so forth, three-membered rings remain significantly underexplored as starting compounds for the synthesis of larger rings except for their involvement into (3+ +2)-cycloadditions.M eanwhile,t hree-membered heterocycles have ah igh potential for organic synthesis;t he high strain energy and facile cleavage of the polarized carbonheteroatom bond ensure their efficient use as synthetic equivalents of 1,3-zwitter-ionic synthon I(Scheme 1a). However,the intensive study of donor-acceptor (D-A) cyclopropanes [4][5][6] during last decades has disproved this belief.Donor and acceptor substituents at the vicinal carbon atoms polarize CÀCb ond between, allowing D-A cyclopropanes to react efficiently as equivalents of synthon I( Scheme 1a). However,the intensive study of donor-acceptor (D-A) cyclopropanes [4][5][6] during last decades has disproved this belief.Donor and acceptor substituents at the vicinal carbon atoms polarize CÀCb ond between, allowing D-A cyclopropanes to react efficiently as equivalents of synthon I( Scheme 1a).…”