Precatalyst-Enabled Selectivity: Enantioselective NiH-Catalyzed anti-Hydrometalative Cyclization of Alkynones to Endo- and Heterocyclic Allylic Alcohols.
Angew Chem Int Ed Engl
; 60(52): 27225-27229, 2021 Dec 20.
Article
in En
| MEDLINE
| ID: mdl-34499395
ABSTRACT
A highly enantioselective NiH-catalyzed hydrocyclization of alkynones with unparalleled anti- and endocyclic selectivities is described. The choice of the precatalysts has significant influence in tuning the regio- and enantioselectivity. Using Ni(OTs)2 /Phox as a precatalyst and (EtO)2 MeSiH as a hydride source, an array of enantioenriched O-, N-, and S-containing heterocyclic tertiary allylic alcohols are obtained in 24-81 % yields with 8020-991 er. Mechanistic investigations and synthetic application are also carried out. This study represents an efficient access to a set of allylic alcohols that are unable to access by the state-of-the-art coupling reactions.
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MEDLINE
Language:
En
Year:
2021
Type:
Article