Asymmetric Organocatalyzed Synthesis of α‐Aminophosphinates via Thiourea Anion‐Binding Catalysis

Thioureas catalyze the reaction of phosphonites with in situ‐generated isoquinolinium salts to give C and P‐stereogenic α‐aminophosphinates in high enantioselectivity (up to 96 %) and yield (up to 95 %). Low diastereoselectivity was obtained and this is rationalized in the context of a mechanistic p...

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Bibliographic Details
Published in:European journal of organic chemistry 2024-03, Vol.27 (11), p.n/a
Main Authors: Niland, Cáoimhe J., Ruddy, Joseph J., O'Fearraigh, Martin P., McGarrigle, Eoghan M.
Format: Article
Language:English
Subjects:
anion-binding
Anions
asymmetric
Binding
Catalysis
Enantiomers
organocatalysis
organophosphorus
Stereoselectivity
thiourea
Thioureas
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Summary:Thioureas catalyze the reaction of phosphonites with in situ‐generated isoquinolinium salts to give C and P‐stereogenic α‐aminophosphinates in high enantioselectivity (up to 96 %) and yield (up to 95 %). Low diastereoselectivity was obtained and this is rationalized in the context of a mechanistic proposal involving anion‐binding catalysis of the P−C bond formation step followed by uncatalyzed Arbuzov collapse. The scope of the reaction, including a g‐scale example, was demonstrated. P‐Stereogenic α‐aminophosphinates were obtained in high enantioselectivity via anion‐binding catalysis with thiourea catalysts, further expanding the range of nucleophiles that can be used in this type of catalysis.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.202301212