Ring Expansion, Photoisomerization, and Retrocyclization of 1,4,2‐Diazaboroles

Su, Bochao; Li, Yongxin; Ganguly, Rakesh; Kinjo, Rei

doi:10.1002/ange.201708720

Cited by 8 publications

(2 citation statements)

References 122 publications

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“…On the other hand, a similar reaction of the imino-Nheterocyclic carbene ligand with MesBBr 2 and subsequent reduction with an excess of KC 8 produced a B,N-dihydroindole derivative 342 as a white solid in 72% yield (Scheme 48). 354 They have proved that the formation of 342 from 341 proceeds via the intermediacy of the B-bromo-analogue of 1,4,2-diazaborole 340.…”

Section: Chemical Reviewsmentioning

confidence: 99%

“…The Al−H stretching frequency (1743 cm −1 ) appears at a significantly lower frequency than that in the base-free AlH 3 (1882.9 cm −1 ). Other examples of NHC-stabilized parent alumane complexes (NHC)AlH 3 (354) were conveniently synthesized by employing either (NMe 3 )AlH 3 or LiAlH 4 as precursors in reactions with imidazolin-2-ylidenes, proceeding through the elimination of NMe 3 or LiH, respectively (Scheme 51). 362,366−369 It is important to mention that until now there is no example of a stable (CAAC)AlH However, due to the high quadrupole moment of the aluminum nucleus, in most cases the NMR signals for the aluminum and the ylidic carbons bound to the aluminum centers were not procurable.…”

Section: Chemical Reviewsmentioning

confidence: 99%

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NHCs in Main Group Chemistry

et al. 2018

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Since the discovery of the first stable N-heterocyclic carbene (NHC) in the beginning of the 1990s, these divalent carbon species have become a common and available class of compounds, which have found numerous applications in academic and industrial research. Their important role as two-electron donor ligands, especially in transition metal chemistry and catalysis, is difficult to overestimate. In the past decade, there has been tremendous research attention given to the chemistry of low-coordinate main group element compounds. Significant progress has been achieved in stabilization and isolation of such species as Lewis acid/base adducts with highly tunable NHC ligands. This has allowed investigation of numerous novel types of compounds with unique electronic structures and opened new opportunities in the rational design of novel organic catalysts and materials. This Review gives a general overview of this research, basic synthetic approaches, key features of NHC-main group element adducts, and might be useful for the broad research community.

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Section: Chemical Reviewsmentioning

confidence: 99%

Section: Chemical Reviewsmentioning

confidence: 99%

NHCs in Main Group Chemistry

et al. 2018

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A Cyclic (Alkyl)(boryl)germylene Derived from a Cyclic (Alkyl)(amino)germylene

Rao

Kinjo

2019

Angewandte Chemie

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Acyclic (alkyl)(amino)germylene undergoes ar ing expansion reaction with dibromomesitylborane (MesBBr 2 )t o affordasix-membered dibromogermane derivative.I nt he presence of Lewis bases (PMe 3 or Me NHC), reduction of the latter with two equivalents of potassium graphite (KC 8 )g ives rise to cyclic (alkyl)(boryl)germylene-Lewis base adducts. Upon heating,t he germylene-PMe 3 adduct reacts with H 2 to yield agermane,probably via abase-free germylene featuring asmall HOMO-LUMO gap.

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Synthesis and Reactivity of Cationic Boron Complexes Distorted by Pyridine‐based Pincer Ligands: Isolation of a Photochemical Hofmann–Martius‐type Intermediate

2020

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A family of cationic boron complexes was synthesized, using a dianilidopyridine pincer ligand, which imposes in‐plane distortion of the geometry at boron towards T‐shaped. Reactivity of these cations toward hydride and base was investigated, and the utility of these cations as precursors to a variety of π‐conjugated BN heterocycles was demonstrated. 300 nm irradiation of a deprotonated pincer boron complex triggered a C−N cleavage/C−C formation yielding a dearomatized boryl imine, which has a structure akin to the long‐proposed intermediate in the photochemical Hofmann–Martius rearrangement. The photo‐rearrangement triggers relief of the distortion imposed by the pincer ligand.

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Ring Expansion, Photoisomerization, and Retrocyclization of 1,4,2‐Diazaboroles

Cited by 8 publications

References 122 publications

NHCs in Main Group Chemistry

NHCs in Main Group Chemistry

A Cyclic (Alkyl)(boryl)germylene Derived from a Cyclic (Alkyl)(amino)germylene

Synthesis and Reactivity of Cationic Boron Complexes Distorted by Pyridine‐based Pincer Ligands: Isolation of a Photochemical Hofmann–Martius‐type Intermediate

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