CC BY-ND-NC 4.0 · Synlett 2019; 30(04): 449-453
DOI: 10.1055/s-0037-1610389
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Complex Boron-Containing Molecules through a 1,2-Metalate Rearrangement/anti-S N 2′ Elimination/Cycloaddition Reaction Sequence

Chloe Tillin
,
Raphael Bigler
,
Renata Calo-Lapido
,
Beatrice S. L. Collins
,
Adam Noble
,
School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK   Email: v.aggarwal@bristol.ac.uk
› Author Affiliations
This work was financially supported by the EPSRC (EP/I038071/1), H2020 ERC (670668), and the University of Bristol. R.B. thanks the Swiss National Science Foundation fellowship program (P2EZP2_165268). R.C.L. was funded by Xunta de Galicia and European Social Fund.
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Publication History

Received: 30 September 2018

Accepted after revision: 25 October 2018

Publication Date:
20 November 2018 (online)


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Published as part of the 30 Years SYNLETT – Pearl Anniversary Issue

Abstract

The three-component coupling of benzylamines, boronic esters, and 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione (PTAD) is reported. The boronate complex formed from an ortho-lithiated benzylamine and a boronic ester undergoes a stereospecific 1,2-metalate rearrangement/anti-S N 2′ elimination in the presence of an N-activator to provide a dearomatized tertiary boronic ester. Interception of this dearomatized intermediate with a dienophile leads to stereopredictable cycloaddition reactions to generate highly complex three-dimensional boron-containing molecular structures. When enantioenriched α-methyl-substituted benzylamines are employed, the corresponding cycloaddition adducts are formed with excellent enantiospecificities.

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