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Synlett 2017; 28(11): 1258-1267
DOI: 10.1055/s-0036-1588772
DOI: 10.1055/s-0036-1588772
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Transition-Metal-Free Boryl Substitution Using Silylboranes and Alkoxy Bases
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
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See refs. 2b, 2c and the following references:
Transition-metal-catalyzed borylations of aryl halides have been reported. For selected examples of Pd-catalyzed reactions, see:
For Ni catalyzed reactions, see:
For a review of transition-metal-catalyzed C(sp2)-H borylations, see:
For pioneering works, see:
For reviews see:
Base-metal-catalyzed borylation reactions have emerged as environmentally benign alternatives to conventional transition-metal-catalyzed borylations because base metals are less toxic and are relatively inexpensive. For Zn-catalyzed reactions, see:
For reviews, see:
For borylation reactions via Lewis base activation of diboron reagents, see:
For electrophilic borylations, see:
For radical-mediated borylations, see:
For reviews, see:
For related halogenophilic reactions, see:
For related halogenophilic reactions with boryl nucleophiles, a few examples have been reported. See, ref 7c and the following references:
For reviews of reactions with silylboranes, see:
For reviews on trace-transition-metal catalysis, see:
For reviews, see:
For a review on the application of AFIR in organic reactions, see:
For pioneering works, see:
For reviews, see:
For selected examples of emissive materials, see:
For selected examples of two-photon absorption materials, see:
For selected examples of ion sensors, see:
For selected examples of electron-transporting materials, see:
For selected examples of nonlinear optical materials, see: