Convenient Route to 2‐(Trialkylstannyl)cyclopropylamines and Their Application in Palladium‐Catalyzed Cross‐Coupling Reactions

Abstract

The 2-(trialkylstannyl)-N,N-dialkylcyclopropylamines 3 were obtained by titanium-mediated aminocyclopropanation of tributylvinylstannane with N,N-dialkylformamides in yields of 80−84% and with excellent diastereoselectivities (trans/cis Ͼ 45:1). The resulting stannanes could advantageously be applied in Stille cross-coupling reactions with aryl iodides, providing the pure trans- 2-aryl-(N,N-dialkylamino)cyclopro-

Ring-opening, cycloaddition and rearrangement reactions of nitrogen-substituted cyclopropane derivatives

“…163,164 However, the related amides or carbamates are usually fairly stable. 165 It is worth noting that 85 is formally a rearranged form of the zwitterion resulting from ringcleavage of 84.…”

Synthesis and Reactivity of Donor-Acceptor Substituted Aminocyclopropanes and Aminocyclobutanes

“…Ring-opening upon single electron transfer oxidation of tertiary cyclopropylamines initiated radical cascade sequences resulting in the formation of diverse polycyclic structures (Scheme 1.54) [208][209][210]. An isolated example of the high reactivity of DA aminocyclopropanes has been reported by de Meijere, Marek and co-workers as they performed a Suzuki coupling between electron poor iodoacrylate 173 and tin-substituted cyclopropylamine 172 (Scheme 1.55) [212]. The fast 5-exo trig cyclization cascade that followed was very rapid and allowed the formation of the cyclic products.…”

Arylcyclopropanes: Properties, Synthesis and Use in Medicinal Chemistry

“…116 In order to overcome the low reactivity of cyclopropylstannyl reagents in the context of cross-coupling reactions, de Meijere utilized conditions that were based on a report by Farina, where a copper co-catalyst was used in conjunction with triphenylarsine and lithium chloride. 117 The amino-cyclopropyl stannyl 208 used in this study was obtained This substrate was then efficiently cross-coupled with different aryl iodides under Farina's conditions, giving the desired arylcyclopropanes 209 in yields ranging from 43% to 67% (Scheme 77). The ortho substituted iodo-toluene was however found to be unreactive under those conditions.…”