Synlett 2017; 28(11): 1258-1267
DOI: 10.1055/s-0036-1588772
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© Georg Thieme Verlag Stuttgart · New York

Transition-Metal-Free Boryl Substitution Using Silylboranes and Alkoxy Bases

Eiji Yamamoto
a  Division of Applied Chemistry & Frontier Chemistry Center, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan
,
Satoshi Maeda
b  Department of Chemistry, Faculty of Science, Hokkaido University, North-10, West-8, Kita-ku, Sapporo 060-0810, Japan   Email: [email protected]
,
Tetsuya Taketsugu
b  Department of Chemistry, Faculty of Science, Hokkaido University, North-10, West-8, Kita-ku, Sapporo 060-0810, Japan   Email: [email protected]
,
Hajime Ito*
a  Division of Applied Chemistry & Frontier Chemistry Center, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan
› Author Affiliations
Further Information

Publication History

Received: 19 February 2017

Accepted after revision: 09 March 2017

Publication Date:
26 April 2017 (online)


Abstract

Silylboranes are used as borylation reagents for organohalides in the presence of alkoxy bases without transition-metal catalysts. PhMe2Si–B(pin) reacts with a variety of aryl, alkenyl, and alkyl halides, including sterically hindered examples, to provide the corresponding organoboronates in good yields with high borylation/silylation ratios, showing good functional group compatibility. Halogenophilic attack of a silyl nucleophile on organohalides, and subsequent nucleophilic attack on the boron electrophile are identified to be crucial, based on the results of extensive theoretical and experimental studies. This boryl­ation reaction is further applied to the first direct dimesitylboryl (BMes2) substitution of aryl halides using Ph2MeSi–BMes2 and Na(O-t-Bu), affording aryldimesitylboranes, which are regarded as an important class of compounds for organic materials.

1 Introduction

2 Boryl Substitution of Organohalides with PhMe2Si–B(pin)/Alkoxy Bases

3 Mechanistic Investigations

4 DFT Mechanistic Studies Using an Artificial Force Induced Reaction (AFIR) Method

5 Dimesitylboryl Substitution of Aryl Halides with Ph2MeSi–BMes2/Na(O-t-Bu)

6 Conclusion

 
  • References

  • 1 Current address: Department of Chemistry, Graduate School of Science, Kyushu University, Motooka 477, Nishi-ku, Fukuoka 819-0395, Japan.

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