Copper-catalysed asymmetric reductive cross-coupling of prochiral alkenes

Abstract

Asymmetric construction of C(sp3)–C(sp3) bond with good stereocontrol of the two connecting carbon centres retaining all carbon or hydrogen substituents is a challenging target in transition metal catalysis. Transition metal-catalysed reductive coupling of unsaturated π-substrates is considered as a potent tool to expediently develop the molecular complexity with high atom efficiency. However, such an asymmetric and intermolecular process has yet to be developed fully. Herein, we report an efficient strategy to reductively couple two prochiral conjugate alkenes using a copper-catalysed tandem protocol in the presence of diboron. Notably, this transformation incorporates a wide range of terminal and internal enynes as coupling partners and facilitates highly diastereo- and enantioselective synthesis of organoboron derivatives with multiple adjacent stereocentres in a single operation.

The potential of converting carbon dioxide to food compounds via asymmetric catalysis

“…This allows for enantioselective synthesis of organoboron derivatives with multiple adjacent stereocenters in the presence of diboron compounds. 26 Another study demonstrated that palladium-based catalysts can catalyze the enantioselective C–H alkylation of allyl groups to yield chiral γ,δ-unsaturated amides. 27 While progress has been made in the formation of asymmetric C–C and asymmetric C–H bonds, a general method has not been fully developed.…”

Asymmetric alkene–alkene reductive cross-coupling reactionviavisible-light photoredox/cobalt dual catalysis

“…5 Recently, Yun disclosed the sole report of a copper-catalyzed asymmetric borylative reductive coupling of two olefins. 6 This strategy is beneficial to address the stereochemical challenges in generating two stereocenters at C(sp 3 )-C(sp 3 ) bonds. However, a new, mild, and compatible approach for the asymmetric reductive coupling of two olefins is highly desirable.…”

“…6 (PC1, 1 mol%), Co(OAc) 2 Á4H 2 O (10 mol%), ligand (12 mol%), NEt 3 (ED, 0.3 mmol), blue LEDs (440 nm) in MeCN (1 mL)…”

Enantioselective and Diastereodivergent Allylation of Propargylic C–H Bonds

“…Given the widespread availability of alkyne derivatives, the enantioselective construction of a C–C or C–X (X = N, O, etc.) bond at the propargylic position is an especially attractive strategy for accessing versatile chiral building blocks en route to stereochemically and functionally complex targets. , However, in contrast to a variety of well-developed protocols that employ prefunctionalized alkyne derivatives for asymmetric propargylation − or metal acetylide precursors for enantioselective nucleophilic addition to synthesize α-chiral alkynes, , the use of simple alkynes for enantioselective propargylic C–H functionalization remains an underdeveloped approach (Scheme A). − …”