TY - JOUR
T1 - Regioselective Functionalization of 9,9-Dimethyl-9-silafluorenes by Borylation, Bromination, and Nitration
AU - Murai, Masahito
AU - Nishinaka, Naoki
AU - Kimura, Mizuki
AU - Takai, Kazuhiko
N1 - Funding Information:
This work is financially supported by a Grant-in-Aid for Scientific Research (C) (no. 16K05778) from MEXT, Japan. The authors gratefully thank Tomonori Shimizu for preliminary studies and also thank Taoka Chemical Co., Ltd. for the gift of 9,9-dimethyl-9-silafluorene.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/5/3
Y1 - 2019/5/3
N2 - Despite the utility of 9-silafluorenes as functional materials and as building blocks, methods for efficient functionalization of their backbone are rare, probably because of the presence of easily cleavable C-Si bonds. Although controlling the regioselectivity of iridium-catalyzed direct borylation of C-H bonds is difficult, we found that bromination and nitration of 2-methoxy-9-silafluorene under mild conditions occurred predominantly at the electron-rich position. The resulting product having methoxy and bromo groups can be utilized as a building block for the synthesis of unsymmetrically substituted 9-silafluorene-containing ?-conjugated molecules.
AB - Despite the utility of 9-silafluorenes as functional materials and as building blocks, methods for efficient functionalization of their backbone are rare, probably because of the presence of easily cleavable C-Si bonds. Although controlling the regioselectivity of iridium-catalyzed direct borylation of C-H bonds is difficult, we found that bromination and nitration of 2-methoxy-9-silafluorene under mild conditions occurred predominantly at the electron-rich position. The resulting product having methoxy and bromo groups can be utilized as a building block for the synthesis of unsymmetrically substituted 9-silafluorene-containing ?-conjugated molecules.
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U2 - 10.1021/acs.joc.9b00598
DO - 10.1021/acs.joc.9b00598
M3 - Article
C2 - 30938531
AN - SCOPUS:85065105012
VL - 84
SP - 5667
EP - 5676
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 9
ER -