Enantiomerically Pure Phosphaalkene-Oxazolines (PhAk-Ox): Synthesis, Scope and Copolymerization with Styrene
作者:Julien Dugal-Tessier、Spencer C. Serin、Emmanuel B. Castillo-Contreras、Eamonn D. Conrad、Gregory R. Dake、Derek P. Gates
DOI:10.1002/chem.201103887
日期:2012.5.14
TripPC(Ph)CMe2Ox (1 b; Trip=2,4,6‐triisopropylphenyl), 2‐iPrC6H4PC(Ph)CMe2Ox (1 c), 2‐tBuC6H4PC(Ph)CMe2Ox (1 d), MesPC(4‐MeOC6H4)CMe2Ox (1 e), MesPC(Ph)C(CH2)4Ox (1 f), and MesPC(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 [Mes
提出了合成一类对映体纯的磷烯烃-恶唑啉(PhAk-Ox)的合成路线的设计。甲硅烷基磷化锂和酮的缩合反应(磷-彼得森反应)用作PC键形成步骤。尝试将PhC(OO)Ox(Ox = CNOCH(i Pr)C H 2)和MesP(SiMe 3)Li缩合得到异常的杂环(MesP)2 C(Ph)CN‐(S)‐CH(i Pr)CH 2 O(3)。但是,通过处理MesP(SiMe 3)成功制备了PhAk-Ox(S,E)-MesPC(Ph)CMe 2 Ox(1 a)。Li与PhC(= O)CMe 2 Ox(52%)。为了证明磷-彼得森合成的模块性和可调谐性,以类似于1 a的方式制备了其他几种磷-烯烃-恶唑啉:TripPC(Ph)CMe 2 Ox(1 b; Trip = 2,4,6-三异丙基苯基) ,2-我PRC 6 ħ 4 PC(PH)CME 2牛(图1c),2-吨BUC 6 ħ 4 PC(PH)CME