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cis ‐ and trans ‐2‐(Isocyanomethyl)‐5,5‐dimethyl‐2‐oxo‐4‐phenyl‐1,3,2‐dioxaphosphorinane – Synthesis and Structure of the First Chiral Isocyanomethylphosphonate Synthons
Author(s) -
Weener JanWillem,
Versleijen Jos P. G.,
Meetsma Auke,
ten Hoeve Wolter,
van Leusen Albert M.
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199808)1998:8<1511::aid-ejoc1511>3.0.co;2-g
Subject(s) - chemistry , synthon , epimer , stereochemistry , dehydration , crystallization , medicinal chemistry , organic chemistry , biochemistry
Both cis ‐2‐(isocyanomethyl)‐5,5‐dimethyl‐2‐oxo‐4‐phenyl‐1,3,2‐dioxaphosphorinane ( 1a ) and the trans epimer 1b have been prepared as potentially useful chiral isocyanomethylphosphonate synthons. 2‐Methoxy‐1,3,2‐dioxaphosphorinanes 5 and the corresponding 2‐ethoxy analog 6 were prepared from 2,2‐dimethyl‐1‐phenyl‐1,3‐propanediol ( 2 ) and were converted in an Arbuzov‐type reaction to 2‐(formamidomethyl)oxo‐1,3,2‐dioxaphosphorinane 7 , which upon dehydration gave 1a . Thus, both (±)‐ 1a and (2 S ,4 S )‐(–)‐ 1a were prepared, and their molecular structures were determined by single‐crystal X‐ray analysis. Treatment of (2 S ,4 S )‐(–)‐ 1a with KF gave a 1:3 equilibrium mixture of the phosphorus epimers 1a and 1b , from which the predominant trans epimer (2 S ,4 R )‐(–)‐ 1b was isolated by column chromatography and crystallization.