Sterically Unprotected Nucleophilic Boron Cluster Reagents

Abstract

We demonstrate that the bench-stable closo-hexaborate cluster dianions can engage in a nucleophilic substitution reaction with a wide array of organic and main-group electrophiles without the use of metal catalysts. The resulting molecules containing B-C bonds can be further converted to tricoordinate boron species widely used in organic synthesis. This strategy showcases a unique substitution and deconstruction reaction sequence with a sterically unprotected nucleophile to afford boronic acid pinacol esters without the use of metal catalysis.

Properties of gaseous closo-[B6X6]2− dianions (X = Cl, Br, I)

“…10 Much less is known about smaller closo-borate dianions. 30 However, the chemistry of hexaborate dianions has recently received a renewed interest [31][32][33] and their salts have been discussed in the context of hydrogen storage. 34,35 In this study, we explore the gas-phase ion properties of hexaborate dianions (closo-[B 6 X 6 ] 2À ).…”

(o‐Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors

“…Although borylsilanes act as borylating reagents,a pplicable substrates are limited to primary alkyl bromides and silylation proceeds as an unavoidable side-reaction. [14] Boron dianion cluster (B 6 H 6 2À )r eacts with primary and secondary sulfonates as well as primary alkyl bromides and iodides to give alkylboronic esters, [15] but only one boron atom in the cluster is consumed for CÀBb ondf ormation and other boron atomsb ecome waste. Recently,t rapping alkyl radical intermediates by diboronc ompounds has opened an ew avenuef or the access to various aliphatic boronic esters ( Figure 1B).…”

Theoretical Study of closo-Borate Anions [BnHn]2− (n = 5–12): Bonding, Atomic Charges, and Reactivity Analysis

“…These cluster species have highly symmetrical structure and unusual chemical bonding, which cannot be described by classical Lewis structure [5][6][7]. closo-borate anions and their derivatives have a lot of useful features such as high stability, low toxicity, and magnetic properties [8][9][10][11]. The main application of closo-borate anions is boron neutron capture therapy of cancer [12][13][14].…”