Pd(II)-Catalyzed Enantioselective Ring-Contraction for the Construction of 1,4-Benzoxazines

Enantioselective ring-contraction reactions have not been widely reported. We have developed an enantioselective ring contraction of 5,6-dihydro-2 H -benzo[ b ][1,4]oxazocines, affording enantiomerically enriched 3,4-dihydro-2 H -1,4-benzoxazine derivatives as single regioisomers. An acidic additive is necessary in order to obtain the products with good yields and enantiomeric ratios (up to 93% yield, 98:2 er). The reaction was successfully performed on a gram scale, and the products can be derivatized easily.