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Synthesis 2022; 54(06): 1566-1576
DOI: 10.1055/a-1681-4720
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Base-Mediated Site-Selective Hydroamination of Alkenes

Ping Li‡
a   Henan Key Lab of Cable Structure and Materials, College of Cable Engineering, Henan Institute of Technology, Xinxiang, 453003, P. R. of China
b   Co-Innovation Center for Efficient Processing and Utilization of Forest Products, College of Chemical Engineering, Nanjing Forestry University, Nanjing, 210037, P. R. of China
c   Department of Chemistry, National University of Singapore, 4 Science Drive 2, 117544, Singapore
,
Boon Chong Lee‡
c   Department of Chemistry, National University of Singapore, 4 Science Drive 2, 117544, Singapore
,
Xiaoxiang Zhang
b   Co-Innovation Center for Efficient Processing and Utilization of Forest Products, College of Chemical Engineering, Nanjing Forestry University, Nanjing, 210037, P. R. of China
,
Ming Joo Koh  ∗
c   Department of Chemistry, National University of Singapore, 4 Science Drive 2, 117544, Singapore
› Author AffiliationsThis research was supported by the Ministry of Education of Singapore Academic Research Fund Tier 1 [grant no. R-143-000-B57-114 (M.J.K.)]. We also thank the National University of Singapore for the continued support of our research program.
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Abstract

We present a base-mediated hydroamination protocol, using substoichiometric amounts of a hydrosilane and potassium tert-butoxide­, that operates under mild conditions at 30 °C. Many aryl- and heteroatom-substituted olefins as well as arylamines are tolerated, affording the desired products with complete regioselectivity. Preliminary mechanistic investigations reveal a non-radical pathway for hydroamination. A sequential remote hydroamination strategy involving an initial Fe-catalysed olefin isomerisation followed by our base-mediated hydroamination was also developed to directly access β-arylamines from terminal aliphatic alkenes.

Key words

hydroamination - remote alkene functionalization - base-mediated - regioselectivity - transition-metal-free

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1681-4720.
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Publication History

Received: 20 September 2021

Accepted after revision: 28 October 2021

Accepted Manuscript online:
28 October 2021

Article published online:
14 December 2021

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