Development and Mechanistic Study of Quinoline-Directed Acyl C–O Bond Activation and Alkene Oxyacylation Reactions

Abstract

The intramolecular addition of both an alkoxy and acyl substituent across an alkene, oxyacylation of alkenes, using rhodium catalyzed C-O bond activation of an 8-quinolinyl ester is described. Our unsuccessful attempts at intramolecular carboacylation of ketones via C-C bond activation ultimately informed our choice to pursue and develop the intramolecular oxyacylation of alkenes via quinoline-directed C-O bond activation. We provide a full account of our catalyst discovery, substrate scope, and mechanistic experiments for quinoline-directed alkene oxyacylation.

Effects of ligands on the migratory insertion of alkenes into rhodium–oxygen bonds

“…[10][11][12] However, related information on the insertions of alkenes into metal-oxygen bonds is lacking. 13,14 The insertions of alkenes into metal-oxygen bonds has been demonstrated to occur during several important catalytic reactions, [15][16][17][18][19][20][21][22][23][24][25][26] including the classic Wacker oxidation under conditions of low chloride concentration, [27][28][29][30][31][32] but examples of discrete complexes that undergo insertions of olens into metalalkoxide bonds are rare and have occurred in most cases with activated alkenes. For example, tetrauoroethene inserts into the platinum(II)-methoxo bond of Pt(DPPE)(OMe)(Me) (Scheme 1A), 33 acrylonitrile inserts into the platinum(II)-phenoxo bond in Pt(PEt 3 ) 2 (OPh)(H), 34 and tetracyanoethene inserts into the Pt(II)-O bond of a platinaoxetane.…”

Palladium‐Catalyzed Selective Carbofunctionalization of Inert γ‐C(sp3)−O Bonds with 4‐Hydroxypyridin‐2(1H)‐ones and 4‐Hydroxy‐2H‐pyran‐2‐ones

“…In recent years, the strategy that involves directing group-assisted regioselective functionalization of C(sp 2 )À O bonds has found great synthetic application value, and great breakthroughs have been achieved in the functionalization of C (sp 2 )À O bonds. [6][7][8][9][10][11] In contrast, the functionalization of unactivated C(sp 3 )À O bonds is still a particularly difficult challenge owing to their relatively high bond dissociation energy (BDE). In a seminal report in 2018, Engle and co-workers explored a new and efficient method to successfully achieve the functionalization of inert C(sp 3 )À O bonds through the cascade of Pd(II)-catalyzed sp 3 CÀ H activation followed by β-O elimination and hydrofunctionalization assisted by the 8-aminoquinolyl directing.…”

Modular and Processable Fluoropolymers Prepared via a Safe, Mild, Iodo–Ene Polymerization

“…The sonication method proved particularly important for 20b , as diene 16 undergoes Cope rearrangement at elevated temperatures. 59 Ester-containing semifluorinated polymer 19a is of particular interest, as it can undergo degradation into 22, which contains only C 6 F 12 units that do not bioaccumulate. 7 We demonstrated the degradation of 19a under basic conditions in solution and on surfaces.…”