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Enantiomerically Pure Phosphaalkene-Oxazolines (PhAk-Ox): Synthesis, Scope and Copolymerization with Styrene

TitleEnantiomerically Pure Phosphaalkene-Oxazolines (PhAk-Ox): Synthesis, Scope and Copolymerization with Styrene
Publication TypeJournal Article
Year of Publication2012
AuthorsDugal-Tessier, J, Serin, SC, Castillo-Contreras, EB, Conrad, ED, Dake, GR, Gates, DP
JournalCHEMISTRY-A EUROPEAN JOURNAL
Volume18
Pagination6349-6359
Date PublishedMAY
ISSN0947-6539
Abstract

{The design of a synthetic route to a class of enantiomerically pure phosphaalkeneoxazolines (PhAk-Ox) is presented. The condensation of a lithium silylphosphide and a ketone (the phospha-Peterson reaction) was used as the P?C bond-forming step. Attempted condensation of PhC(?O)Ox (Ox=CNOCH(iPr)CH2) and MesP(SiMe3)Li gave the unusual heterocycle (MesP)2C(Ph)?CN-(S)-CH(iPr)CH2O (3). However, PhAk-Ox (S,E)-MesP?C(Ph)CMe2Ox (1?a) was successfully prepared by treating MesP(SiMe3)Li with PhC(?O)CMe2Ox (52?%). To demonstrate the modularity and tunability of the phospha-Peterson synthesis several other phosphaalkeneoxazolines were prepared in an analogous manner to 1?a: TripP?C(Ph)CMe2Ox (1?b; Trip=2,4,6-triisopropylphenyl), 2-iPrC6H4P?C(Ph)CMe2Ox (1?c), 2-tBuC6H4P?C(Ph)CMe2Ox (1?d), MesP?C(4-MeOC6H4)CMe2Ox (1?e), MesP?C(Ph)C(CH2)4Ox (1?f), and MesP?C(3,5-(CF3)2C6H3)C(CH2)4Ox (1?g). To evaluate the PhAk-Ox compounds as prospective precursors to chiral phosphine polymers, monomer 1?a and styrene were subjected to radical-initiated copolymerization conditions to afford {[}\{MesPC(Ph)(CMe2Ox)\}x\{CH2CHPh\}y]n (9?a: x=0.13n

DOI10.1002/chem.201103887