Catalytic Asymmetric 1,2-Addition of α-Isothiocyanato Phosphonates: Synthesis of Chiral β-Hydroxy- or β-Amino-Substituted α-Amino Phosphonic Acid Derivatives

α‐Amino phosphonic acid derivatives are considered to be the most important structural analogues of α‐amino acids and have a very wide range of applications. However, approaches for the catalytic asymmetric synthesis of such useful compounds are very limited. In this work, simple, efficient, and ver...

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Published in:Angewandte Chemie (International ed.) 2014-02, Vol.53 (7), p.1862-1866
Main Authors: Cao, Yi-Ming, Shen, Fang-Fang, Zhang, Fu-Ting, Zhang, Jin-Long, Wang, Rui
Format: Article
Language:English
Subjects:
asymmetric synthesis
Catalysis
Cyanates - chemistry
Molecular Structure
organocatalysis
Organophosphonates - chemistry
Phosphorous Acids - chemical synthesis
Phosphorous Acids - chemistry
Stereoisomerism
synthetic methods
α-amino phosphonic acids
α-isothiocyanato compounds
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Summary:α‐Amino phosphonic acid derivatives are considered to be the most important structural analogues of α‐amino acids and have a very wide range of applications. However, approaches for the catalytic asymmetric synthesis of such useful compounds are very limited. In this work, simple, efficient, and versatile organocatalytic asymmetric 1,2‐addition reactions of α‐isothiocyanato phosphonate were developed. Through these processes, derivatives of β‐hydroxy‐α‐amino phosphonic acid and α,β‐diamino phosphonic acid, as well as highly functionalized phosphonate‐substituted spirooxindole, can be efficiently constructed (up to 99 % yield, d.r. >20:1, and >99 % ee). This novel method provides a new route for the enantioselective functionalization of α‐phosphonic acid derivatives. Correct chirality critical: Organocatalytic asymmetric Adol‐type and Mannich‐type reactions of α‐isothiocyanato phosphonate have been realized. Michael addition was also applicable under the same catalytic conditions. This versatile approach provides a new route for the synthesis of diverse highly optically active functionalized α‐amino phosphonic acid derivatives.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201308514