Stereoselectivities and regioselectivities of (4 + 3) cycloadditions between allenamide-derived chiral oxazolidinone-stabilized oxyallyls and furans: experiment and theory.

ABSTRACT: A systematic investigation of the regioselectivities and stereoselectivities of (4 + 3) cycloadditions between unsymmetrical furans and a chiral oxazolidinone-substituted oxyallyl is presented. Cycloadditions were performed using an oxyallyl containing a (R)-4-phenyl-2-oxazolidinone auxiliary (2(Ph)), under either thermal or ZnCl(2)-catalyzed conditions. Reactions of 2(Ph) with 2-substituted furans gave syn cycloadducts selectively, while cycloadditions with 3-substituted furans gave selectively anti cycloadducts. The stereoselectivities were in favor of a single diastereoisomer (I) in all but one case (2-CO(2)R). Density functional theory calculations were performed to explain the selectivities. The results support a mechanism in which all cycloadducts are formed from the E isomer of the oxyallyl (in which the oxazolidinone C?O and oxyallyl oxygen are anti to each other) or the corresponding (E)-ZnCl(2) complex. The major diastereomer is derived from addition of the furan to the more crowded face of the oxyallyl. Crowded transition states are favored because they possess a stabilizing CH-? interaction between the furan and the Ph group.

SUBMITTER: Antoline JE 

PROVIDER: S-EPMC3174849 | biostudies-literature | 2011 Sep

REPOSITORIES: biostudies-literature