Enantioselective Synthesis of α-Aryl-β-Aminocyclopropane Carboxylic Acid Derivatives via Rh(II)-Catalyzed Cyclopropanation of Vinylsulfonamides with α-Aryldiazoesters

Abstract

The reaction of vinylsulfonamides with donor–acceptor carbenes derived from α-aryldiazoesters, catalyzed by the tert-butyl glycine-derived dirhodium complex Rh2(S-4-Br-NTTL)4, has been reported. This method provides a variety of α-aryl-β-aminocyclopropane carboxylic acid derivatives bearing one quaternary carbon stereogenic center vicinal to the amino-substituted carbon in high yields with excellent diastereo- and enantioselectivities. Vinylsulfonamides showed complementary advantages over the well-developed vinylamides or vinylcarbamates for this Rh­(II)-catalyzed cyclopropanation strategy. Moreover, these conformationally restricted α-aryl-β-aminocyclopropyl carboxylic acid derivatives can be readily incorporated into dipeptides.

Rapid Olefin Cyclopropanation Catalyzed by a Bioinspired Cobalt Complex

“…Among the methods available for the synthesis of cyclopropanes, transition-metal-catalyzed cyclopropanation of olefins with diazo compounds offers the most robust and atom-efficient approach. [4] To date, a handful of catalytic methods based on this concept have employed a wide range of transition metals including copper, [9,10] rhodium, [11][12][13][14][15] ruthenium, [16,17] cobalt, [18][19][20] gold, [21,22] silver, [23,24] iridium, [25,26] and osmium. [27] Due to their economic and efficient properties, cobalt catalysts have garnered increasing attention.…”

Stereoselective Cyclopropanation of Multisubstituted Enesulfinamides: Asymmetric Construction of α-Tertiary Cyclopropylamine Derivatives Containing β-Quaternary Stereocenters

“…To circumvent the need for preassembled strained ring systems, direct enantioenriched cyclopropylamine formation from acyclic substrates has emerged as a complementary approach in recent years . Noteworthy examples include catalytic asymmetric processes involving titanium-mediated reductive cyclopropanation of N , N -dialkyl carboxamides or nitriles (Scheme B) as well as chiral rhodium­(II)- or gold­(I)-catalyzed cyclopropanation of functionalized enamines or their equivalents using in situ formed metallo carbenoids (Scheme C) . While the former method allows for rapid access to racemic cyclopropylamines from simple substrates, the development of its asymmetric version utilizing chiral titanium catalysts is still in its early stages, with only moderate stereocontrol achieved thus far (Scheme B). , In the latter methods, high enantiocontrol is commonly achieved by employing chiral precious metal (Rh and Au) complexes as catalysts.…”

Asymmetric cyclopropanation of electron-rich alkenes by the racemic diene rhodium catalyst: the chiral poisoning approach

“…Noteworthily, the literature examples of asymmetric cyclopropanation of such substrates are still rather limited. 16–20…”