A Straightforward Synthesis of Benzestrol by Matteson Homologation Using Chiral Benzyl Carbamates

A straightforward and highly stereoselective synthesis of the non‐steroidal estrogen benzestrol is described based on Matteson homologations. Starting from a chiral arylboronic ester two classical Matteson reactions allow the introduction of two stereogenic centers, while the third one is transferred from a chiral benzyl carbamate under retention. Protodeboration and deprotection provide benzestrol in only 6 steps and an overall yield of 30%.