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Borane-induced ring closure reaction of oligomethylene-linked bis-allenes
The trimethylene-linked bis-allene 3a reacts with Piers' borane [HB(C(6)F(5))(2)] by a hydroboration/allylboration sequence to generate the cyclization product 5a. Its pyridine adduct was isolated and characterized by X-ray diffraction. Compound 5a undergoes a typical frustrated Lewis pair 1,2-...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8148058/ https://www.ncbi.nlm.nih.gov/pubmed/34084385 http://dx.doi.org/10.1039/c9sc03870a |
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author | Tao, Xin Škoch, Karel Daniliuc, Constantin G. Kehr, Gerald Erker, Gerhard |
author_facet | Tao, Xin Škoch, Karel Daniliuc, Constantin G. Kehr, Gerald Erker, Gerhard |
author_sort | Tao, Xin |
collection | PubMed |
description | The trimethylene-linked bis-allene 3a reacts with Piers' borane [HB(C(6)F(5))(2)] by a hydroboration/allylboration sequence to generate the cyclization product 5a. Its pyridine adduct was isolated and characterized by X-ray diffraction. Compound 5a undergoes a typical frustrated Lewis pair 1,2-P/B alkene addition reaction with PPh(3) to give the heterobicyclic bridged olefinic zwitterionic product 9a. The tetramethylene-linked bis-allene 3b and its phenylene annulated analogue 3c react with HB(C(6)F(5))(2) to give the analogous seven-membered ring products 5b,c under mild conditions. The cyclization product 5a undergoes a series of sequential allylboration reactions with two equivalents of allene followed by ring-closure to give the four-component coupling product 12a. It undergoes FLP addition to an exo-methylene group upon treatment with PPh(3). Compound 12a is oxidatively converted to the boron-free alcohol. |
format | Online Article Text |
id | pubmed-8148058 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81480582021-06-02 Borane-induced ring closure reaction of oligomethylene-linked bis-allenes Tao, Xin Škoch, Karel Daniliuc, Constantin G. Kehr, Gerald Erker, Gerhard Chem Sci Chemistry The trimethylene-linked bis-allene 3a reacts with Piers' borane [HB(C(6)F(5))(2)] by a hydroboration/allylboration sequence to generate the cyclization product 5a. Its pyridine adduct was isolated and characterized by X-ray diffraction. Compound 5a undergoes a typical frustrated Lewis pair 1,2-P/B alkene addition reaction with PPh(3) to give the heterobicyclic bridged olefinic zwitterionic product 9a. The tetramethylene-linked bis-allene 3b and its phenylene annulated analogue 3c react with HB(C(6)F(5))(2) to give the analogous seven-membered ring products 5b,c under mild conditions. The cyclization product 5a undergoes a series of sequential allylboration reactions with two equivalents of allene followed by ring-closure to give the four-component coupling product 12a. It undergoes FLP addition to an exo-methylene group upon treatment with PPh(3). Compound 12a is oxidatively converted to the boron-free alcohol. The Royal Society of Chemistry 2019-12-18 /pmc/articles/PMC8148058/ /pubmed/34084385 http://dx.doi.org/10.1039/c9sc03870a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Tao, Xin Škoch, Karel Daniliuc, Constantin G. Kehr, Gerald Erker, Gerhard Borane-induced ring closure reaction of oligomethylene-linked bis-allenes |
title | Borane-induced ring closure reaction of oligomethylene-linked bis-allenes |
title_full | Borane-induced ring closure reaction of oligomethylene-linked bis-allenes |
title_fullStr | Borane-induced ring closure reaction of oligomethylene-linked bis-allenes |
title_full_unstemmed | Borane-induced ring closure reaction of oligomethylene-linked bis-allenes |
title_short | Borane-induced ring closure reaction of oligomethylene-linked bis-allenes |
title_sort | borane-induced ring closure reaction of oligomethylene-linked bis-allenes |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8148058/ https://www.ncbi.nlm.nih.gov/pubmed/34084385 http://dx.doi.org/10.1039/c9sc03870a |
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