The stereospecific ring-opening of O-heterocycles to provide acyclic alcohols and carboxylic acids with controlled formation of a new C-C bond is reported. These reactions provide new methods for synthesis of acyclic polyketide analogs with complex stereochemical arrays. Stereoselective synthesis of the cyclic template is utilized to control relative configuration; subsequent stereospecific nic...

The century-old fluoresceins and rhodamines persist as flexible scaffolds for fluorescent and fluorogenic compounds. Extensive exploration of these xanthene dyes has yielded general structure-activity relationships where the development of new probes is limited only by imagination and organic chemistry. In particular, replacement of the xanthene oxygen with silicon has resulted in new red-shift...

Abstract Polar reactive organometallic species have been key reagents in synthesis for more than a century. Stereodefined 1,2-dimetallated alkenes offer promising synthetic utility; however, few methods are available their preparation due to relatively low stability. Here we report the reductive anti -1,2-dimetallation of alkynes stereoselectively generate trans -1,2-dimagnesio- and 1,2-dialumi...