[reaction: see text]. A new tether for small molecule synthesis is reported. This functionally active tether mediates the desymmetrization of a pseudo-C(2)-symmetric tris-allylic phosphate triester to generate a P-chiral bicyclo[4.3.1]phosphate containing ample steric and stereoelectronic differentiation for investigating chemo-, regio-, and stereoselective transformations. Overall, the method reported herein demonstrates a fundamentally new role of phosphates in synthesis and provides differentiated polyol building blocks for use in natural product synthesis.

The first synthesis of dolabelide C (1), a cytotoxic marine macrolide, is reported utilizing a phosphate tether-mediated approach. Bicyclic phosphates (S,S,SP)-5 and (R,R,RP)-5 serve as the central building blocks for the construction of two major 1,3-anti-diol subunits in 1 through selective cleavage pathways, regioselective olefin reduction and cross-metathesis. Overall, phosphate-mediated processes provided copious amounts of both major subunits allowing for a detailed RCM macrocyclization study to the 24-membered macrolactone 1.

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[structure: see text]. We report a new methodology for the construction of novel and uniquely shaped 3-azabicyclo[4.2.0]octan-4-one derivatives by combining the Ugi multicomponent reaction with [2+2] enone-olefin photochemical transformations. The overall sequence is capable of creating up to five stereocenters; however, in most cases, only two diastereomers are observed.