Inter‐Element Boration Reactions of Carbon‐Carbon Multiple Bonds via Lewis‐Basic Activation of Boron Reagents

Abstract

Here, we review recent progress in transition‐metal‐free inter‐element boration reactions via Lewis‐basic activation of various boron reagents, focusing mainly on the boration reactions of carbon‐carbon multiple bonds without an electron‐withdrawing (activating) group and those with an electron‐withdrawing group where the polarity of the addition reaction is inverse to the “natural” reactivity.

Scaffold-Retained Structure Generator to Exhaustively Create Molecules in an Arbitrary Chemical Space

“…As synthetic organic chemistry has advanced, , the syntheses of molecules located in the chemical spaces that have yet to be sufficiently studied, as well as their applications to medicinal chemistry, have become increasingly popular. − ,− ,− For the virtual screening of these molecules, it is necessary to construct a VL of molecules with unique substructures.…”

Bis(neopentylglycolato)diboron (B2nep2) as a bidentate ligand and a reducing agent for early transition metal chlorides giving MCl4(B2nep2) complexes

“…The superior reducing ability of such sp 2 –sp 3 diboron adducts is ascribed to the strong σ-donating character of the other boryl substituent on the sp 3 -configurated boron atom that negatively shifts the redox potential. 4 In fact, treatment of commercially available B 2 pin 2 and B 2 nep 2 with inorganic and organic anions produces anionic sp 2 –sp 3 diboron adducts as the key intermediates with strong reducing ability. 5…”

A Hydride‐Substituted Homoleptic Silylborate: How Similar is it to its Diborane(6)‐Dianion Isostere?

“…In a similar vein, disilanes, especially the highly reactive Si 2 Cl 6 , are currently establishing themselves as useful reagents for the preparation of organosilanes with a wide range of applications, for example, in silicone chemistry [3] . The next systematic step in the extension of this chemistry is the progression from homoelement compounds to the corresponding heteroelement compounds, namely silylboranes R 2 B−SiR’ 3 [2b,4] . Silylboranes are suitable for the introduction of boryl and/or silyl groups into a given substrate molecule (Scheme 1).…”

“…[3] The next systematic step in the extension of this chemistry is the progression from homoelement compounds to the corresponding heteroelement compounds, namely silylboranes R 2 B−SiR’ 3 . [ 2b , 4 ] Silylboranes are suitable for the introduction of boryl and/or silyl groups into a given substrate molecule (Scheme 1 ). As an example, Ito and coworkers used pinB−SiMe 2 Ph ( A ) as storage form of the [Bpin] − anion, which they released in situ by heterolysis of the B−Si bond with KOMe to prepare B .…”