Rhodium‐Mediated Stoichiometric Synthesis of Mono‐, Bi‐, and Bis‐1,2‐Azaborinines: 1‐Rhoda‐3,2‐azaboroles as Reactive Precursors
| Autor: | Theresa Dellermann, Ivo Krummenacher, Holger Braunschweig, Merlin Heß |
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| Rok vydání: | 2021 |
| Předmět: |
cyclization
azaborinines 010405 organic chemistry Chemistry Communication structure elucidation Organic Chemistry Hot Paper chemistry.chemical_element Aromaticity General Chemistry 010402 general chemistry 01 natural sciences Communications Catalysis 0104 chemical sciences Rhodium chemistry.chemical_compound metallacycles Polymer chemistry Structural isomer nitrogen heterocycles ddc:546 Stoichiometry Phosphine |
| Zdroj: | Chemistry (Weinheim an Der Bergstrasse, Germany) |
| ISSN: | 1521-3765 0947-6539 |
| Popis: | A series of highly substituted 1,2‐azaborinines, including a phenylene‐bridged bis‐1,2‐azaborinine, was synthesized from the reaction of 1,2‐azaborete rhodium complexes with variously substituted alkynes. 1‐Rhoda‐3,2‐azaborole complexes, which are accessible by phosphine addition to the corresponding 1,2‐azaborete complexes, were also found to be suitable precursors for the synthesis of 1,2‐azaborinines and readily reacted with alkynyl‐substituted 1,2‐azaborinines to generate new regioisomers of bi‐1,2‐azaborinines, which feature directly connected aromatic rings. Their molecular structures, which can be viewed as boron‐nitrogen isosteres of biphenyls, show nearly perpendicular 1,2‐azaborinine rings. The new method using rhodacycles instead of 1,2‐azaborete complexes as precursors is shown to be more effective, allowing the synthesis of a wider range of 1,2‐azaborinines. Boron‐nitrogen analogs of metallacyclopentadienes in the form of 1‐rhoda‐3,2‐azaboroles (see Figure) are shown to be suitable precursors for the synthesis of 1,2‐azaborinines. Comparisons with 1,2‐azaborete rhodium complexes demonstrate their superior reactivity towards alkynes, allowing to expand the range of 1,2‐azaborinines. A series of multiply substituted 1,2‐azaborinines, including a phenylene‐bridged derivative and rare bicyclic derivatives composed of two 1,2‐azaborinine rings linked by a single bond, are reported. |
| Databáze: | OpenAIRE |
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