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 rhodium vinylidenes through 1,2-silicon migration, followed by 1,3-carbon (alkyne) migration via the formation of hypervalent silicon centers.
Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.
Tomoya
T
Namba
Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.
Susumu
S
Kawauchi
Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.
Yu
Y
Shibata
Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.|Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo, 184-8588, Japan.
Hiroshi
H
Kanno
Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.|Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo, 184-8588, Japan.
Ken
K
Tanaka
alkynes; benzoxasiloles; cycloisomerization; migration reactions; rhodium