Synthesis of Alkynylmethylidene‐benzoxasiloles through a Rhodium‐Catalyzed Cycloisomerization Involving 1,2‐Silicon and 1,3‐Carbon Migration

It is shown that a cationic rhodium(I)/biphep complex catalyzes the cycloisomerization of 2‐(alkynylsilylethynyl)phenols, leading to alkynylmethylidene‐benzoxasiloles through concomitant silicon and carbon migration. This unprecedented cycloisomerization presumably proceeds via the formation of rhod...

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Bibliographic Details
Published in:Angewandte Chemie 2017-03, Vol.129 (11), p.3050-3054
Main Authors: Namba, Tomoya, Kawauchi, Susumu, Shibata, Yu, Kanno, Hiroshi, Tanaka, Ken
Format: Article
Language:English
Subjects:
Alkine
Alkynes
Benzoxasilole
Carbon
Carbon cycle
Catalysis
Cationic
Chemical synthesis
Chemistry
Cycloisomerisierungen
Formations
Isomerization
Migration
Phenols
Rhodium
Silicon
Umlagerungen
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Summary:It is shown that a cationic rhodium(I)/biphep complex catalyzes the cycloisomerization of 2‐(alkynylsilylethynyl)phenols, leading to alkynylmethylidene‐benzoxasiloles through concomitant silicon and carbon migration. This unprecedented cycloisomerization presumably proceeds via the formation of rhodium vinylidenes through 1,2‐silicon migration, followed by 1,3‐carbon (alkyne) migration via the formation of hypervalent silicon centers. Unerwartete Reise: Ein kationischer Rhodium(I)‐Biphep‐Komplex katalysiert die Cycloisomerisierung von 2‐(Alkinylsilylethinyl)phenolen zu Alkinylmethyliden‐Benzoxasilolen. Wahrscheinlich entstehen dabei Rhodiumvinylidene über eine 1,2‐Si‐Verschiebung; anschließend folgt eine 1,3‐Alkin‐Verschiebung unter Bildung eines hypervalenten Siliciumzentrums.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201612560