XBphos-Rh: a halogen-bond assembled supramolecular catalyst

Abstract

XBphos-Rh constitutes the first example of halogen bonding as the driving force behind the assembly of a transition-metal catalyst for hydroborations.

Cobalt‐Catalyzed Regio‐ and Stereoselective Hydroboration of Allenes

“…Compared with previous approaches to allylic boronic acid derivatives, [3] transition-metal-catalyzed hydroboration of readily available allenes with pinacolborane (HBpin) would be, in principle, a very efficient method featuring excellent atom economy. However, compared with the well-established catalytic hydroboration of alkenes, [4] alkynes, [5] and 1,3-dienes, [3b, 6] the hydroboration of allenes has remained underdeveloped. [7,8] In 2009, a one-pot two-step reaction to form homoallylic alcohols involving non-catalytic hydroboration of alkyl-substituted terminal allenes with a chiral borane reagent was reported, however, the stereoselectivity is rather poor (Scheme 1 a).…”

La[N(SiMe3)2]3‐Catalyzed Hydroboration of Esters and Other Challenging Unsaturated Groups

“…In the past few years, the hydroboration of alkynes has been relatively mature. Some transition metal catalysts, non‐transition metal catalysis, and metal‐free systems have been developed in succession. However, these systems required metal catalysts in addition where appropriate amount of alkali, ligands or other adducts are usually added to in order to get better results.…”

On the Interplay between Charge‐Shift Bonding and Halogen Bonding

“…Halogen bond (XB) interactions are prevalent in many areas of chemistry, [1][2][3][4][5][6][7] demonstrating important applications in catalysis, [8][9][10][11] crystal engineering [12][13][14] and rational drug design. Halogen bond (XB) interactions are prevalent in many areas of chemistry, [1][2][3][4][5][6][7] demonstrating important applications in catalysis, [8][9][10][11] crystal engineering [12][13][14] and rational drug design.…”

“…The anisotropy of the electron density distribution in a covalently bonded halogen atom (X) can induce a site of attractive interactions with a nucleophilic region from another, or from the same, molecular entity. Halogen bond (XB) interactions are prevalent in many areas of chemistry, [1][2][3][4][5][6][7] demonstrating important applications in catalysis, [8][9][10][11] crystal engineering [12][13][14] and rational drug design. [15][16][17][18] From a fundamental point of view, it has as well become a topic of main interest in the computational chemistry community.…”