Enantioselective palladium(0)-catalyzed intramolecular cyclopropane functionalization: access to dihydroquinolones, dihydroisoquinolones and the BMS-791325 ring system

Abstract

Enantioselective palladium(0)-catalyzed C–H arylations of cyclopropanes provide efficient access to dihydroquinolones, dihydroisoquinolones and the BMS-791325 indolobenzazepine core.

Rhodium‐Catalyzed Enantioselective Silylation of Cyclopropyl C−H Bonds

“…Yu and co‐workers reported enantioselective, Pd‐catalyzed arylation and alkylation reactions of cyclopropanes containing N ‐aryl or triflyl amides as a directing group with organoborane or iodoarene reagents . In addition, Cramer and co‐workers reported Pd‐catalyzed intramolecular arylations and alkylations of cyclopropyl C−H bonds to form tetrahydroquinolines, dihydroquinolones, dihydroisoquinolones, and γ‐lactams . However, enantioselective functionalization to form products containing a new carbon–heteroatom bond has not been reported.…”

Chiral Catalysts for Pd0‐Catalyzed Enantioselective C−H Activation

“…The enantioselective activation of cyclopropane C−H bonds was later extended to substrates containing amide linkers ( 24 – 25 , Scheme 11 b). [47] The same phosphoramidite ligand L 9 was found to promote the cyclization of both anilide ( 24 ) and amide ( 25 ) compounds with high enantioselectivity and yield across a wide range of substrates.…”

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

“…Three years later, this methodology was extended to allow the synthesis of dihydroquinolones (92 to 93) and dihydroisoquinolones (94 to 95). 110 In this case, the same TADDOL-derived phosphoramidite ligand L33 from their earlier study could be employed, and by simply inverting the amide connectivity in the reactants, . Further investigation also identified chiral bisphosphine monoxide L36 as a promising ligand for this transformation, affording the cyclized product in 88% ee but a reduced 37% yield.…”