TY - JOUR
T1 - Direct alkoxysilylation of alkoxysilanes for the synthesis of explicit alkoxysiloxane oligomers
AU - Wakabayashi, Ryutaro
AU - Tamai, Misa
AU - Kawahara, Kazufumi
AU - Tachibana, Hiroki
AU - Imamura, Yutaka
AU - Nakai, Hiromi
AU - Kuroda, Kazuyuki
N1 - Funding Information:
We thank Prof. R. Laine (University of Michigan) for his comments which have greatly improved the manuscript We also thank Dr. T. Shibue and Mr. N. Sugimura (MCCL, Waseda University) for the help in NMR and MS measurements. This work was supported in part by a Grant-in-Aid for Scientific Research (No. 23245044 ) and the Global COE program “Practical Chemical Wisdom” from MEXT, Japan . K. Kawahara is grateful for financial support provided through a Grant-in-Aid for JSPS Fellow from MEXT . K. Kuroda also acknowledges the support by Elements Science and Technology Project “Functional Designs of Silicon-Oxygen-Based Compounds by Precise Synthetic Strategies” from MEXT, Japan.
PY - 2012/10/1
Y1 - 2012/10/1
N2 - Direct alkoxysilylation, which is a powerful tool to provide explicit alkoxysiloxanes, is developed and its versatility is investigated. Siloxane pentamers Si[OSiR 1(OMe) 2] 4 having various functional groups (R 1 = methyl, vinyl, phenyl, chloropropyl and n-butyl groups) were successfully obtained by direct alkoxysilylation of Si(OR) 4 (R = t-Bu, CHPh 2). Thus, the versatility of the reaction is confirmed on organic functional groups R 1. Functional group tolerance of the reaction is discussed on the basis of electronegativity of the R 1 groups. Alkoxysilylation of Si(Ot-Bu) 2(OMe) 2 and Si(Ot-Bu)(OMe) 3 selectively gives trimer (MeO) 2Si[OSiMe(OMe) 2] 2 and dimer (MeO) 3SiOSiMe(OMe) 2, respectively. Thus, the feasibility on siloxane structure is also confirmed. Various siloxane compounds are synthesized by this newly developed reaction for the first time.
AB - Direct alkoxysilylation, which is a powerful tool to provide explicit alkoxysiloxanes, is developed and its versatility is investigated. Siloxane pentamers Si[OSiR 1(OMe) 2] 4 having various functional groups (R 1 = methyl, vinyl, phenyl, chloropropyl and n-butyl groups) were successfully obtained by direct alkoxysilylation of Si(OR) 4 (R = t-Bu, CHPh 2). Thus, the versatility of the reaction is confirmed on organic functional groups R 1. Functional group tolerance of the reaction is discussed on the basis of electronegativity of the R 1 groups. Alkoxysilylation of Si(Ot-Bu) 2(OMe) 2 and Si(Ot-Bu)(OMe) 3 selectively gives trimer (MeO) 2Si[OSiMe(OMe) 2] 2 and dimer (MeO) 3SiOSiMe(OMe) 2, respectively. Thus, the feasibility on siloxane structure is also confirmed. Various siloxane compounds are synthesized by this newly developed reaction for the first time.
KW - Alkoxysilanes
KW - Lewis acids
KW - Nonhydrolytic synthesis
KW - Siloxanes
KW - Sol-gel processes
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U2 - 10.1016/j.jorganchem.2012.05.033
DO - 10.1016/j.jorganchem.2012.05.033
M3 - Article
AN - SCOPUS:84865020417
SN - 0022-328X
VL - 716
SP - 26
EP - 31
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
ER -