Enantioselective
Ni-catalyzed reductive aryl monofluoroalkenylation
of alkenes between aryl bromides and gem-difluoroalkenes
has been developed. The reaction proceeding under room temperature
and base-free reaction conditions tolerates a wide range of functional
groups on both coupling partners. Various synthetically useful oxindoles
containing monofluoroalkenyl substituent are obtained in good yields
with 85%–95% enantiomeric excess. In addition, the synthetic
method can be further applied to the late-stage monofluoroalkenylation
of complex biologically active compounds.
Spirocycles play an important role in drug discovery and development owing to their inherent three-dimensionality and structural novelty. Despite the recent significant progress, the straightforward catalytic asymmetric assembly of spirocyclic scaffolds with multiple stereocenters from readily available starting materials remains a formidable challenge. Herein, we develop an unprecedented nickel-catalyzed one-pot synthesis of enantioenriched spiroindanones from easily available 1,6-enynes and oformylarylboronic acids. The reaction proceeds smoothly under redox-neutral conditions, without the need for an additional hydrogen donor, and features a broad substrate scope and excellent regio-, enantio-, and diastereoselectivity.
An unprecedented nickel-catalyzed domino reductive cyclization of alkynes and o-bromoaryl aldehydes is described. The reaction features broad substrate scope and is tolerant of a variety of functional groups, providing straightforward access to biologically significant indanones and spiroindanone pyrrolidine derivatives in good yields with excellent regio-and diastereoselectivity. Preliminary mechanistic studies have shown that indanones are formed by the cyclization of o-bromoaryl aldehydes and alkynes to form indenol intermediates, followed by hydrogen autotransfer.
An unprecedented nickel-catalyzed domino reductive cyclization of alkynes and o-bromoaryl aldehydes is described. The reaction features broad substrate scope and is tolerant of a variety of functional groups, providing straightforward access to biologically significant indanones and spiroindanone pyrrolidine derivatives in good yields with excellent regio-and diastereoselectivity. Preliminary mechanistic studies have shown that indanones are formed by the cyclization of o-bromoaryl aldehydes and alkynes to form indenol intermediates, followed by hydrogen autotransfer.
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