Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis

Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis

A new method for the synthesis of α-branched amines by reductive functionalization of tertiary carboxamides and lactams is described. The process relies on the efficient and controlled reduction of tertiary amides by a sodium hydride/sodium iodide composite, in situ treatment of the resulting anioni...

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Main Authors: Ong, Derek Yiren, Fan, Dongyang, Dixon, Darren J., Chiba, Shunsuke
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2022
Subjects:
Science::Chemistry
Amines
Coupling Reactions
Online Access:https://hdl.handle.net/10356/154835
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-1548352023-02-28T19:58:31Z Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis Ong, Derek Yiren Fan, Dongyang Dixon, Darren J. Chiba, Shunsuke School of Physical and Mathematical Sciences Science::Chemistry Amines Coupling Reactions A new method for the synthesis of α-branched amines by reductive functionalization of tertiary carboxamides and lactams is described. The process relies on the efficient and controlled reduction of tertiary amides by a sodium hydride/sodium iodide composite, in situ treatment of the resulting anionic hemiaminal with trimethylsilyl chloride and subsequent coupling with nucleophilic reagents including Grignard reagents and tetrabutylammonium cyanide. The new method exhibits broad functional-group compatibility, operates under transition-metal-free reaction conditions, and is suitable for various synthetic applications on both sub-millimole and on multigram scales. Ministry of Education (MOE) Nanyang Technological University Accepted version This work was supported by funding from Nanyang Technological University (NTU) (for S.C.), the Singapore Ministry of Education (Academic Research Fund Tier 2: MOE2017-T2-1-064 for S.C.). 2022-01-13T07:30:02Z 2022-01-13T07:30:02Z 2020 Journal Article Ong, D. Y., Fan, D., Dixon, D. J. & Chiba, S. (2020). Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis. Angewandte Chemie International Edition, 59(29), 11903-11907. https://dx.doi.org/10.1002/anie.202004272 1433-7851 https://hdl.handle.net/10356/154835 10.1002/anie.202004272 32329555 2-s2.0-85084856709 29 59 11903 11907 en MOE2017-T2-1-064 Angewandte Chemie International Edition This is the peer reviewed version of the following article: Ong, D. Y., Fan, D., Dixon, D. J. & Chiba, S. (2020). Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis. Angewandte Chemie International Edition, 59(29), 11903-11907, which has been published in final form at https://doi.org/10.1002/anie.202004272. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. application/pdf
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Science::Chemistry
Amines
Coupling Reactions
spellingShingle Science::Chemistry
Amines
Coupling Reactions
Ong, Derek Yiren
Fan, Dongyang
Dixon, Darren J.
Chiba, Shunsuke
Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis
description A new method for the synthesis of α-branched amines by reductive functionalization of tertiary carboxamides and lactams is described. The process relies on the efficient and controlled reduction of tertiary amides by a sodium hydride/sodium iodide composite, in situ treatment of the resulting anionic hemiaminal with trimethylsilyl chloride and subsequent coupling with nucleophilic reagents including Grignard reagents and tetrabutylammonium cyanide. The new method exhibits broad functional-group compatibility, operates under transition-metal-free reaction conditions, and is suitable for various synthetic applications on both sub-millimole and on multigram scales.
author2 School of Physical and Mathematical Sciences
author_facet School of Physical and Mathematical Sciences
Ong, Derek Yiren
Fan, Dongyang
Dixon, Darren J.
Chiba, Shunsuke
format Article
author Ong, Derek Yiren
Fan, Dongyang
Dixon, Darren J.
Chiba, Shunsuke
author_sort Ong, Derek Yiren
title Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis
title_short Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis
title_full Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis
title_fullStr Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis
title_full_unstemmed Transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis
title_sort transition-metal-free reductive functionalization of tertiary carboxamides and lactams for α-branched amine synthesis
publishDate 2022
url https://hdl.handle.net/10356/154835
_version_ 1759855643041202176

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