Switchable, Reagent‐Controlled Diastereodivergent Photocatalytic Carbocyclisation of Imine‐Derived α‐Amino Radicals

Abstract

Ar eagent-controlled stereodivergent carbocyclisation of aryl aldimine-derived, photocatalytically generated, aamino radicals possessing adjacent conjugated alkenes,affording either bicyclic or tetracyclic products,i sd escribed. Under net reductive conditions using commercial Hantzsche ster,t he a-amino radical species underwent as ingle stereoselective cyclisation to give trans-configured amino-indane structures in good yield, whereas using as ubstituted Hantzsch ester as am ilder reductant afforded cis-fused tetracyclic tetrahydroquinoline frameworks,r esulting from two consecutive radical cyclisations.J udicious choice of the reaction conditions allowed libraries of both single and dual cyclisation products to be synthesised with high selectivity,n otable predictability, and good-to-excellent yields.C omputational analysis employing DFT revealed the reaction pathway and mechanistic rationale behind this finely balanced yet readily controlled photocatalytic system.

Π–Π Stacking Complex Induces Three‐Component Coupling Reactions To Synthesize Functionalized Amines

“…The formation of complex amines via three‐component reactions intrigued us to achieve cyclic amines via intramolecular C−C bond formation reactions. For this purpose, under the model reaction conditions, α,β‐unsaturated ester‐tethered benzaldehydes were investigated to assess 1‐aminoindanes, which can be used as intermediates for the construction of pharmaceutical compounds [29d] . Indeed, the reaction system was effective in providing trans ‐1‐aminoindanes in moderate yields with both electron‐rich and ‐deficient aniline derivatives (Figure 6, 7 a – 7 f ).…”

Solvent-Controlled Switchable Synthesis of gem-Difluoro Compounds from Anhydrides under Photoredox Catalysis

“…In addition to changing chemistry, the way chemists approach this subject is also constantly evolving. Unconventional, yet valuable concepts have been introduced into the field, including but not limited to late-stage functionalization, 12 atom economy, 13,14 bifunctional reagents, 15 divergent syntheses, [16][17][18][19][20] and multicomponent reactions. 21 Indeed, these strategies allow scientists to access broader chemical space for achieving synthetic endeavors.…”