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.
A copper‐catalyzed chemodivergent approach to five‐ and six‐membered benzocycles from dienyl arenes tethered with a ketone has been developed. Through proper choice of coordinating ligands and catalytic conditions, copper‐catalyzed borylative cyclization of a single dienyl arene can be diverted to two different pathways, leading to indanols and dihydronaphthalenols with high stereoselectivity. The chiral bidentate bisphosphine ligand (S,S)‐Ph‐BPE was optimal for asymmetric copper‐allyl addition to a tethered ketone via a boat‐like transition state, whereas NHC ligands led to boro‐allyl addition producing indanols with high diastereoselectivity.
We report a copper-catalyzed asymmetric reductive coupling
of vinyl
boronates with imines, which directly access enantiomerically enriched
β-aminoalkylboronates. Stereoselective addition of the in situ
generated chiral α-borylalkyl copper to N-phosphinoyl
imines provided target products in good yields with high diastereo-
and enantioselectivity. Vinyl boronate with methylated acenaphthoquinone
as a boron ligand was essential to efficiently spawn asymmetric products,
and organic transformations of the boron moiety, along with the easily
removable N-protecting group, proved their synthetic
utility.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.