Litcius/Paper detail

Catalyst Controlled Site- and Stereoselective Rhodium(II) Carbene C(sp<sup>3</sup>)–H Functionalization of Allyl Boronates

Yannick T. Boni, Janakiram Vaitla, Huw M. L. Davies

2022Organic Letters10 citationsDOI

Abstract

Rhodium(II) catalyst-controlled site- and stereoselective carbene insertion into the distal allylic C(sp3)–H bond of allyl boronates is reported. The optimum chiral catalyst for this reaction is Rh2(S-TPPTTL)4. The fidelity and asymmetric induction of this catalytic transformation allows for a highly diastereoselective and enantioselective C–C bond formation without interference from the allyl boronate functionality. The resulting functionalized allyl boronates are susceptible to stereoselective allylations, generating products with control of stereochemistry at four contiguous stereogenic centers.

Topics & Concepts

StereocenterChemistryStereoselectivityCarbeneRhodiumAllylic rearrangementEnantioselective synthesisCatalysisStereochemistryAsymmetric inductionMedicinal chemistryOrganic chemistryCatalytic C–H Functionalization MethodsCyclopropane Reaction MechanismsSynthetic Organic Chemistry Methods