Copper‐Catalyzed Triboration: Straightforward, Atom‐Economical Synthesis of 1,1,1‐Triborylalkanes from Terminal Alkynes and HBpin

A convenient and efficient one‐step synthesis of 1,1,1‐triborylalkanes was achieved via sequential dehydrogenative borylation and double hydroborations of terminal alkynes with HBpin (HBpin=pinacolborane) catalyzed by inexpensive and readily available Cu(OAc)2. This process proceeds under mild conditions, furnishing 1,1,1‐tris(boronates) with wide substrate scope, excellent selectivity, and good functional‐group tolerance, and is applicable to gram‐scale synthesis without loss of yield. The 1,1,1‐triborylalkanes can be used in the preparation of α‐vinylboronates and borylated cyclic compounds, which are valuable but previously rare compounds. Different alkyl groups can be introduced stepwise via base‐mediated deborylative alkylation to produce racemic tertiary alkyl boronates, which can be readily transformed into useful tertiary alcohols. Bpin it: A practical, atom‐economical method for the synthesis of 1,1,1‐triborylalkanes based on sequential dehydrogenative borylation and double hydroboration of terminal alkynes with HBpin is described. The 1,1,1‐triborylalkane products are useful synthetic intermediates for the construction of multiple C−C and C−O bonds to give carbocyclic organoboronates and unsymmetric tertiary alcohols.