Chiral Spirophosphoric-Acid-Catalyzed Divergent Vinylogous Mannich and aza-Friedel-Crafts Reactions of 2-Methoxyfuran

Yi Han Chao; Paru Jamwal; Gunda Ananda Rao; Ramani Gurubrahamam; Kwunmin Chen

doi:10.1021/acs.orglett.4c01458

Chiral Spirophosphoric-Acid-Catalyzed Divergent Vinylogous Mannich and aza-Friedel-Crafts Reactions of 2-Methoxyfuran

Yi Han Chao, Paru Jamwal, Gunda Ananda Rao, Ramani Gurubrahamam^*, Kwunmin Chen^*

^*此作品的通信作者

化學系

研究成果: 雜誌貢獻 › 期刊論文 › 同行評審

摘要

The first enantioselective vinylogous Mannich reaction is developed using 2-methoxyfuran under chiral spirophosphoric acid catalysis. The strategy involves 4-isoxazoline derivatives as cyclic ketimine surrogates and provides γ-butenolide scaffolds (up to 97% ee and >20:1 dr). The mechanistic investigations suggest that an in situ generated water molecule plays a crucial role in delivering γ-butenolide, while the use of molecular sieves delivers aza-Friedel-Crafts products. The synthetic utility of γ-butenolide is shown toward obtaining piperidone skeleton via a lactone-lactam rearrangement.

原文	英語
頁（從 - 到）	4938-4944
頁數	7
期刊	Organic Letters
卷	26
發行號	23
DOIs	https://doi.org/10.1021/acs.orglett.4c01458
出版狀態	已發佈 - 2024 6月 14

ASJC Scopus subject areas

生物化學
物理與理論化學
有機化學

存取文件

10.1021/acs.orglett.4c01458

其它文件與鏈接

CCDC 2297399: Experimental Crystal Structure Determination
Chao, Y. (Contributor), Jamwal, P. (Contributor), Ananda Rao, G. (Contributor), Gurubrahamam, R. (Contributor) & Chen, K. (Contributor), Cambridge Crystallographic Data Centre, 2024
DOI: 10.5517/ccdc.csd.cc2h3mnx, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2h3mnx&sid=DataCite
資料集: Dataset

引用此

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abstract = "The first enantioselective vinylogous Mannich reaction is developed using 2-methoxyfuran under chiral spirophosphoric acid catalysis. The strategy involves 4-isoxazoline derivatives as cyclic ketimine surrogates and provides γ-butenolide scaffolds (up to 97% ee and >20:1 dr). The mechanistic investigations suggest that an in situ generated water molecule plays a crucial role in delivering γ-butenolide, while the use of molecular sieves delivers aza-Friedel-Crafts products. The synthetic utility of γ-butenolide is shown toward obtaining piperidone skeleton via a lactone-lactam rearrangement.",

author = "Chao, {Yi Han} and Paru Jamwal and {Ananda Rao}, Gunda and Ramani Gurubrahamam and Kwunmin Chen",

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AU - Chao, Yi Han

AU - Jamwal, Paru

AU - Ananda Rao, Gunda

AU - Gurubrahamam, Ramani

AU - Chen, Kwunmin

PY - 2024/6/14

Y1 - 2024/6/14

N2 - The first enantioselective vinylogous Mannich reaction is developed using 2-methoxyfuran under chiral spirophosphoric acid catalysis. The strategy involves 4-isoxazoline derivatives as cyclic ketimine surrogates and provides γ-butenolide scaffolds (up to 97% ee and >20:1 dr). The mechanistic investigations suggest that an in situ generated water molecule plays a crucial role in delivering γ-butenolide, while the use of molecular sieves delivers aza-Friedel-Crafts products. The synthetic utility of γ-butenolide is shown toward obtaining piperidone skeleton via a lactone-lactam rearrangement.

AB - The first enantioselective vinylogous Mannich reaction is developed using 2-methoxyfuran under chiral spirophosphoric acid catalysis. The strategy involves 4-isoxazoline derivatives as cyclic ketimine surrogates and provides γ-butenolide scaffolds (up to 97% ee and >20:1 dr). The mechanistic investigations suggest that an in situ generated water molecule plays a crucial role in delivering γ-butenolide, while the use of molecular sieves delivers aza-Friedel-Crafts products. The synthetic utility of γ-butenolide is shown toward obtaining piperidone skeleton via a lactone-lactam rearrangement.

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Chiral Spirophosphoric-Acid-Catalyzed Divergent Vinylogous Mannich and aza-Friedel-Crafts Reactions of 2-Methoxyfuran

摘要

ASJC Scopus subject areas

存取文件

其它文件與鏈接

指紋

資料集

CCDC 2297399: Experimental Crystal Structure Determination

引用此