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The asymmetric synthesis of P-stereogenic phosphinates through allylic alkylation of H-phosphinates has been developed. With H-phosphinates and allylic acetates as the starting materials, a variety of allylic P-chiral phosphinates were accessed in high enantioselectivities of up to 92% ee and generally high yields. In addition, a further study demonstrated the applicability of this protocol, including the scale-up synthesis and facile transformation of chiral products from phosphinates to phosphine oxides with organolithium reagents under mild reaction conditions.

The asymmetric synthesis of

Herein we report a Rh(I)-catalyzed two carbon insertion into C-C bonds of benzocyclobutenols by employing symmetrical and unsymmetrical allenes. This reaction provides rapid access to alkylidene tetralins bearing two adjacent stereogenic centers in good yields and diasteroselectivities.

An efficient first approach to the Stemona alkaloid (+/-)-Stemonamine has been developed on the basis of a key TiCl4 promoted tandem Semipinacol rearrangement/Schmidt reaction and a Dieckmann condensation reaction.