Cargando…

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-...

Descripción completa

Detalles Bibliográficos
Autores principales: Tao, Xin, Škoch, Karel, Daniliuc, Constantin G., Kehr, Gerald, Erker, Gerhard
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2019
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
_version_ 1783697768311685120
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
work_keys_str_mv AT taoxin boraneinducedringclosurereactionofoligomethylenelinkedbisallenes
AT skochkarel boraneinducedringclosurereactionofoligomethylenelinkedbisallenes
AT daniliucconstanting boraneinducedringclosurereactionofoligomethylenelinkedbisallenes
AT kehrgerald boraneinducedringclosurereactionofoligomethylenelinkedbisallenes
AT erkergerhard boraneinducedringclosurereactionofoligomethylenelinkedbisallenes