Synthesis of Catechol‐, Pinacol‐, and Neopentylglycolborane through the Heterogeneous Catalytic BB Hydrogenolysis of Diboranes(4)

Abstract

A new synthetic approach to hydroboranes catechol-, pinacol-, and neopentylglycolborane has been developed. Starting from diboranes(4) B2cat2, B2pin2, or B2neop2, the respective boranes were obtained by heterogeneously catalyzed cleavage of the B-B bond in the respective diboranes with hydrogen. Group 10 metals were found to be effective catalysts for this reaction.

The Borole Route to Reactive Pentafluorophenyl‐Substituted Diboranes(4)

“…[14] We could experimentally observe the formation of the HB(C 6 F 5 ) 2 dimer.F or ac omplete analysis we trapped the resulting pairs of B À Hb oranes by in situ hydroboration of tertbutylacetylene. [14] We could experimentally observe the formation of the HB(C 6 F 5 ) 2 dimer.F or ac omplete analysis we trapped the resulting pairs of B À Hb oranes by in situ hydroboration of tertbutylacetylene.…”

Formation and Reactivity of Electron‐Precise B−B Single and Multiple Bonds

“…(37), diamino(diaryl)- (40), and (tetraamino)diborane(4) compounds (41 a-c)c an undergo two-electron reduction to the corresponding diborate dianions (Scheme 10 c,d). One-and two-electronr eductionso fdiborane(4) compounds.…”

“…[40] Asimilar method had already been employed in one isolated instance by the group of Hartwig to generate deuterated DBPin by iridiumcatalyzed deuteration of B 2 Pin 2 . [40] Asimilar method had already been employed in one isolated instance by the group of Hartwig to generate deuterated DBPin by iridiumcatalyzed deuteration of B 2 Pin 2 .…”

Boron−Boron Dehydrocoupling of Boranes Initiated by Reaction with Iodine

“…Although low‐barrier boron–boron‐dehydrocoupling reactions are not unprecedented (see the example reported by Fontaine and co‐workers in ref. ), the presence of a catalyst is generally required in most known examples . In contrast, a decrease of the reaction barrier for the dehydrocoupling reaction was already observed in the case of [(RS(H)B(μ‐hpp)] 2 , which eliminates H 2 at room temperature (Scheme ) …”

“…Braunschweig, Marder and co‐workers. reported the catalytic dehydrocoupling of catechol and pinacol borane . Weller and co‐workers reported the dehydrogenative boron‐homocoupling reaction of amine‐borane at a Rh atom .…”