Metal‐Free Conversion of Methane and Cycloalkanes to Amines and Amides by Employing a Borylnitrene

Hydrogen and Amine Activation by a Frustrated Lewis Pair of a Bulky N‐Heterocyclic Carbene and B(C6F5)3

“…[32,33] The presence and necessity of the carbene in the formation of 6-8 suggests that these reactions are catalytic in carbene, and indeed formation is readily accomplished with the use of 2-3 mol % of ItBu. In these cases, the quantitative formation of the aminoboranes [33,34] is complete within 2 h at 25 8C. Notably, 6-8 are stable in solution under these conditions.…”

Catalyst‐Free Formal Thioboration to Synthesize Borylated Benzothiophenes and Dihydrothiophenes

“…The use of ClBpin as an alternative electrophilic boron reagent, which would theoretically provide direct access to the desired pinacolboronic ester 3 from 1 , was not evaluated because of its instability above −35 °C and its difficulty of synthesis. [21] …”

Pinacolatoboron fluoride (pinBF) is an efficient fluoride transfer agent for diastereoselective synthesis of benzylic fluorides

“…B-Chloro-1,3-dioxa-2-boracyclopentane, 31,32 B-chloro-4,4,5,5-tetramethyl-1,3-dioxa-2-boracyclopentane (pinBCl) 33 and B-chloro-1,3-dioxa-2-boracyclohexane 34 have previously been prepared by treatment of the corresponding diols with BCl 3 , although the analogous preparation of the fluorine analogues has not been reported. In the event, initial attempts at the use of this protocol with BF 3 ÁOEt 2 were not successful, and therefore an alternative was sought.…”