ABSTRACT
A highly chemoselective and enantioselective cyclization of γ-chloroenals and ketimines has been developed to synthesize enantiopure 3,4-2H-pyrindin-2-ones as major products. It is proposed that the intermediate enone IV reacted with an enamine to proceed with a [3 + 3] cyclization, thereby affording 3,4-2H-pyrindin-2-ones as major products. Interestingly, the addition of LiCl promoted the formation of the enamine and accelerated the [3 + 3] cyclization. In contrast, the [4 + 2] cycloaddition reaction between the intermediate vinyl enolate VIII and an imine offered 5,6-2H-pyrindin-2-ones as minor products. This protocol represents the exceptional potential of N-heterocyclic carbene (NHC) catalytic reactions in accessing biologically active 3,4-2H-pyrindin-2-one derivatives in good yield with high chemoselectivities and excellent enantiomeric purities.
ABSTRACT
A chiral N-heterocyclic carbene (NHC)-catalyzed [4 + 2] annulation of γ-chloroenals and α-arylidene pyrazolinones was developed in the absence of expensive oxidants. The reaction proceeds smoothly via a vinyl enolate intermediate to afford spirocyclohexane pyrazolones in moderate to good yield (up to 86%) with high diastereoselectivities (up to 15:1 dr) and excellent enantioselectivities (up to >99% ee).
ABSTRACT
A chiral N-heterocyclic carbene-catalyzed benzoin condensation reaction in water has been developed, affording α-hydroxy ketones in good to high yields and high enantioselectivities. Water was proposed as a proton shuttle in the aqueous asymmetric condensation reaction.
ABSTRACT
A chiral NHC-catalyzed cycloaddition of γ-fluoroenals is developed. The nucleophilic γ-carbon generated via C-F bond cleavage undergoes highly enantioselective cycloaddition (up to >99% ee) to isatins and provides 3'-spirocyclic oxindoles in good yields (up to 91%).
ABSTRACT
Elimination/[3+2] cycloaddition reactions of simple enals and unprotected isatins with haloamides have been developed. This transformation provides rapid access to highly functionalized oxazolidin-4-ones that are represented in bioactive compounds.