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Oxygen‐Substituted Isocyanates: Blocked (Masked) Isocyanates Enable Controlled Reactivity
Author(s) -
Ivanovich Ryan A.,
Polat Dilan E.,
Beauchemin André M.
Publication year - 2017
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201701046
Subject(s) - isocyanate , chemistry , hydroxylamine , reactivity (psychology) , oxygen , polymer chemistry , combinatorial chemistry , organic chemistry , polyurethane , medicine , alternative medicine , pathology
Abstract Oxygen‐substituted isocyanates ( O ‐isocyanates) are rare isocyanates with a reported propensity to trimerize, a side‐reaction that severely limited their use in synthesis. Herein, the development of blocked (masked) O ‐isocyanate precursors that form this reactive intermediate in situ provide controlled reactivity, allowing the first examples of cascade reactions involving O ‐isocyanates. Complex hydroxylamine‐derived hydantoins and dihydrouracil compounds can be rapidly assembled from α‐ and β‐amino esters, illustrating the convenience of masked O ‐isocyanates as hydroxylamine derived building blocks. Evidence for the intermediacy of an O ‐isocyanate intermediate is provided.