Monobenzofused 1,4-Azaborines: Synthesis, Characterization, and Discovery of a Unique Coordination Mode

We report the first general synthesis of boron‐substituted monobenzofused 1,4‐azaborines using ring‐closing metathesis of an enamine‐containing diene as a key synthetic strategy. As part of our investigations, we discovered that the B‐C3 moiety in a 1,4‐azaborine can serve uniquely as a η2‐L‐type li...

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Published in:Angewandte Chemie International Edition 2014-06, Vol.53 (26), p.6795-6799
Main Authors: Xu, Senmiao, Haeffner, Fredrik, Li, Bo, Zakharov, Lev N., Liu, Shih-Yuan
Format: Article
Language:English
Subjects:
Aromatic compounds
Aza Compounds - chemistry
Azaborine
BN heterocycle
boron
Boron - chemistry
Boron Compounds - chemical synthesis
Boron Compounds - chemistry
Catalysts
coordination complex
Coordination Complexes - chemical synthesis
Coordination Complexes - chemistry
Crystallography, X-Ray
Crystals
Decomposition reactions
Dienes
Diffraction
Ligands
Molecular Conformation
Palladium - chemistry
phosphine
Phosphines
Platinum
Synthesis
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Summary:We report the first general synthesis of boron‐substituted monobenzofused 1,4‐azaborines using ring‐closing metathesis of an enamine‐containing diene as a key synthetic strategy. As part of our investigations, we discovered that the B‐C3 moiety in a 1,4‐azaborine can serve uniquely as a η2‐L‐type ligand. This functionality is exemplified by two κ2‐N‐η2‐BC Pt complexes of a boron‐pyridyl‐substituted monobenzofused‐1,4‐azaborine. Single‐crystal X‐ray diffraction analysis of the Pt complexes shows a strong structural contribution from the iminium resonance form of the monobenzofused‐1,4‐azaborine ligand. We also demonstrate that a palladium(0) complex supported by a 1,4‐azaborine‐based phosphine ligand can catalyze hydroboration of 1‐buten‐3‐yne with unique selectivity. In view of the importance of arene–metal π‐interactions in catalytic applications, this work should open new opportunities for ligand design involving the 1,4‐azaborine motif as an arene substitute. Breaking N‐BC News: The first general synthesis of boron‐substituted monobenzofused 1,4‐azaborines has been developed. As part of the synthetic investigations, a unique κ2‐N‐η2‐BC coordination mode was discovered and investigated.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201403903