A Spiro Phosphamide Catalyzed Enantioselective Proton Transfer of Ylides in a Free Carbene Insertion into N−H Bonds

Free carbene readily causes multiple side reactions due to its high energy, thus its asymmetric transformation is very difficult. We present here our findings of high‐pKa Brønsted acid catalysts that enable free carbene insertion into N−H bonds of amines to prepare chiral α‐amino acid derivatives wi...

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Vydáno v:	Angewandte Chemie International Edition Ročník 62; číslo 15; s. e202300691 - n/a
Hlavní autoři:	Pan, Jia‐Bin, Zhang, Xuan‐Ge, Shi, Yi‐Fan, Han, Ai‐Cui, Chen, Yu‐Jia, Ouyang, Jing, Li, Mao‐Lin, Zhou, Qi‐Lin
Médium:	Journal Article
Jazyk:	angličtina
Vydáno:	WEINHEIM Wiley 03.04.2023 Wiley Subscription Services, Inc
Vydání:	International ed. in English
Témata:	Amines Amino acids Asymmetric Catalysis Brønsted Acids Carbenes Catalysts Chemistry Chemistry, Multidisciplinary Computer applications Enantiomers Insertion Intermediates Irradiation N−H Insertion Organic chemistry Phosphamides Physical Sciences Protons Science & Technology Side reactions Bronsted Acids PALLADIUM Asymmetric Catalysis ACIDITIES ACIDS N-H Insertion DIAZO-COMPOUNDS Phosphamides Carbenes Brønsted Acids N−H Insertion
ISSN:	1433-7851, 1521-3773, 1521-3773
On-line přístup:	Získat plný text
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Shrnutí:	Free carbene readily causes multiple side reactions due to its high energy, thus its asymmetric transformation is very difficult. We present here our findings of high‐pKa Brønsted acid catalysts that enable free carbene insertion into N−H bonds of amines to prepare chiral α‐amino acid derivatives with high enantioselectivity. Under irradiation with visible light, diazo compounds produce high‐energy free carbenes that are captured by amines to form free ylide intermediates, and then the newly designed high‐pKa Brønsted acids, chiral spiro phosphamides, promote the proton transfer of ylides to afford the products. Computational and kinetic studies uncover the principle for the rational design of proton‐transfer catalysts and explain how the catalysts accelerate this transformation and provide stereocontrol. A highly enantioselective free carbene insertion into the N−H bond of amines has been achieved. Newly designed high‐pKa Brønsted acid catalysts, chiral spiro phosphamides, were found to be key and promote the proton transfer of the ylide intermediates and control the enantioselectivity of the reaction. The reaction provides a new approach to amino acid derivatives.
Bibliografie:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23
ISSN:	1433-7851 1521-3773 1521-3773
DOI:	10.1002/anie.202300691