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By‐Product‐Free Siloxane‐Bond Formation and Programmed One‐Pot Oligosiloxane Synthesis
Author(s) -
Matsumoto Kazuhiro,
Sajna Kappam Veettil,
Satoh Yasushi,
Sato Kazuhiko,
Shimada Shigeru
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201611623
Subject(s) - hydrosilylation , siloxane , iridium , silylation , chemistry , catalysis , polymer chemistry , coupling reaction , boron , condensation reaction , hydrolysis , organic chemistry , polymer
Siloxane bonds are usually synthesized by condensation reactions, such as hydrolysis/dehydration and cross‐coupling reactions, in which the generation of by‐products during bond formation can not be avoided. We have developed a one‐pot sequence of iridium‐catalyzed silyl ester hydrosilylation and boron‐catalyzed rearrangement of the resulting disilyl acetals for the construction of siloxane bonds, in principle without the formation of any by‐products. Moreover, the programmed synthesis of tri‐, tetra‐, and pentasiloxanes was possible in a single flask by combining the above sequence of iridium‐catalyzed hydrosilylation and boron‐catalyzed rearrangement with a boron‐catalyzed cross‐coupling reaction. The obtained oligosiloxanes are difficult to synthesize selectively by other known synthetic procedures.