P/N-Heteroleptic Cu(I)-Photosensitizer-Catalyzed [3 + 2] Regiospecific Annulation of Aminocyclopropanes and Functionalized Alkynes

Abstract

We report here a regiospecific [3 + 2] annulation between aminocyclopropanes and various functionalized alkynes enabled by a P/N-heteroleptic Cu(I) photosensitizer under photoredox catalysis conditions. Thus, a divergent construction of 3-aminocyclopentene derivatives including methylsulfonyl-, arylsulfonyl-, chloro-, ester-, and trifluoromethyl-functionalized aminocyclopentenes could be achieved with advantages of high regioselectivity, broad substrate compatibility, and mild and environmentally benign reaction conditions.

Light-induced homolysis of copper(ii)-complexes – a perspective for photocatalysis

“…Evidence for LIH via a dissociative LMCT involving a Cu( i ) → Cu(0) transition was put forward by Liu and co-workers 53 for the [3 + 2]-cycloaddition of N -arylaminocyclopropanes 176 with alkynes 177, mirroring the transformation described by Verma, Reiser and coworkers 37 via Cu( ii )/Cu( i ) cycles ( cf. Scheme 16 ) ( Scheme 26 ).…”

Approach to Access Benzo[j]phenanthridinones from 1,7-Enynes and Aryldiazonium Salts via a Domino Radical Relay Process Enabled by a P/N-Heteroleptic Cu(I)-Photosensitizer

“…To the best of our knowledge, the utility of 2-substituent-free 1, n -enynes to construct aromatic bicycles by radical species having the dual role of an initiator and a terminator has never been determined. With our ongoing research interest in the construction of polycyclic compounds from 1, n -enynes and the development of highly efficient photocatalytic reactions involving P/N-heteroleptic Cu­(I)-photosensitizers, ,, we herein describe a facile and novel approach to access benzo­[ j ]­phenanthridinones from 2-substituent-free 1,7-enynes and aryldiazonium salts via a domino radical relay process enabled by a P/N-heteroleptic Cu­(I)-photosensitizer under relatively mild reaction conditions [Scheme c­(3)].…”

Room-Temperature CuI-Catalyzed N-Arylation of Cyclopropylamine

“…Moreover, many lead and drug candidates containing the N -(hetero)­aryl cyclopropylamine moiety have been recently designed and synthesized, including potent Takeda G-protein-coupled receptor 5 (TGR5) agonists, an orally active and nonsteroidal farnesoid X receptor (FXR) antagonist, a topoisomerase inhibitor, and a modulator of α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) receptor (Figure A). (ii) N -(Hetero)­aryl cyclopropylamines are building blocks or key intermediates to access various novel ring systems in organic synthesis, e.g., the photocycloadditions of N -(hetero)­aryl cyclopropylamines to alkenes, alkynes, or bicyclo­[1,1,0]­butanes to design various molecular skeletons (Figure B). − Hence, the development of effective methods for preparing N -(hetero)­aryl cyclopropylamines is necessary and many endeavors have been made regarding this for decades.…”