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Metal-free borylative dearomatization of indoles: exploring the divergent reactivity of aminoborane CH borylation catalysts

Metal-free borylative dearomatization of indoles: exploring the divergent reactivity of... While the dearomatization of indoles by carbonboron bond forming reactions is new and quite promising, they are so far mainly metal-catalyzed. Here, we establish the use of metal-free catalysts in promoting such reactions in an atom-efficient way. The in situ generated ambiphilic aminoborane catalyst (1-Pip-2-BH2-C6H4)2 (Pip = piperidyl) promotes borylative dearomatization of various 1-arylsulfonyl indoles with pinacolborane in a syn addition fashion, with H and Bpin groups added respectively to the 2 and 3 positions of indoles. Catalysis proceeds with good to excellent conversion and essentially with complete regio- and diastereoselectivity. From mechanistic insights and DFT computations, we realized and established that prototypical boranes can also catalyze this borylative dearomatization. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chemical Science Royal Society of Chemistry

Metal-free borylative dearomatization of indoles: exploring the divergent reactivity of aminoborane CH borylation catalysts

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Publisher
Royal Society of Chemistry
Copyright
This journal is © The Royal Society of Chemistry
ISSN
2041-6520
DOI
10.1039/c8sc01093e
Publisher site
See Article on Publisher Site

Abstract

While the dearomatization of indoles by carbonboron bond forming reactions is new and quite promising, they are so far mainly metal-catalyzed. Here, we establish the use of metal-free catalysts in promoting such reactions in an atom-efficient way. The in situ generated ambiphilic aminoborane catalyst (1-Pip-2-BH2-C6H4)2 (Pip = piperidyl) promotes borylative dearomatization of various 1-arylsulfonyl indoles with pinacolborane in a syn addition fashion, with H and Bpin groups added respectively to the 2 and 3 positions of indoles. Catalysis proceeds with good to excellent conversion and essentially with complete regio- and diastereoselectivity. From mechanistic insights and DFT computations, we realized and established that prototypical boranes can also catalyze this borylative dearomatization.

Journal

Chemical ScienceRoyal Society of Chemistry

Published: May 17, 2018

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