The ring-opening metathesis polymerization (ROMP) of (+)-Vince lactam [(S)-azabicyclo[2.2.1]hept-5-en-3-one] (1) and its N-benzyl, N-trimethylsilyl (TMS), and N-tert-butoxycarbonyl (Boc) derivatives (2a–c) is reported. Highly cis-syndiotactic (st) poly(Vince lactam) was readily accessible by using the cyclometalated ruthenium complex Ru[CH(2-OiPr-Ph)](Piv)(1-mesityl-3-C₄H₈-imidazol-2-ylidene) (Piv =2,2-dimethylpropanoate) (4); however, small amounts of trans double bonds (ca. 5%) formed. Highly cis-st (>98%) polymers were accessible by the action of the monoaryloxide pyrrolide (MAP) type complexes W(N-2,6-iPr₂C₆H₃)(CHCMe₂Ph)(Pyr)(HMTO) (Pyr = pyrrolide, HMTO = 2,6-(2,4,6-Me₃C₆H₂)₂C₆H₃O) (7) and W(O)(CHCMe₂Ph)(PMe₂Ph)(Me₂Pyr)(TPPO) (TPPO = 2,3,5,6-tetraphenylphenolate) (8). Complementary, cis-isotactic (>98% cis-it) polymers were prepared by the action of Mo(N-2,6-Me₂C₆H₃)(CHCMe₂Ph)(OBiphen) (OBiphen = 3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-1,1′-biphenyl-2,2′-diolate) (5) and its tungsten analogue W(N-2,6-Me₂C₆H₃)(CHCMe₂Ph)(OBiphen) (6). Notably, none of these Mo- and W-based initiators polymerize unprotected Vince lactam. Deprotection of poly(N-TMS Vince lactam) and poly(N-Boc Vince lactam) with neat trifluoroacetic acid allowed for the isolation of all-cis highly tactic poly(Vince lactam).

中文翻译：

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对映体纯Vince内酰胺的区域和立体选择性开环易位聚合。

（+）-文斯内酰胺[（S）-氮杂双环[2.2.1]庚-5-烯-3-酮]（1）及其N-苄基，N-三甲基甲硅烷基的开环复分解聚合（ROMP）（1）TMS），和ñ -叔丁氧羰基（BOC）衍生物（2a-c中报道）。高度顺式-间同立构（ST）聚（文斯内酰胺）是通过使用环金属钌络合物茹容易获得[CH（2-OiPr-PH）]（PIV）（1-均三甲苯基3-C ₄ H ^ ₈咪唑-2- -亚叉基）（Piv = 2,2-二甲基丙酸酯）（4）; 但是，少量的反式形成双键（约5％）。通过单芳氧基吡咯化物（MAP）型配合物W（N-2,6- i Pr ₂ C ₆ H ₃）（CHCMe ₂ Ph）（Pyr）（HMTO）的作用可得到高顺式-st（> 98％）聚合物）（Pyr =吡咯化物，HMTO = 2,6-（2,4,6-Me ₃ C ₆ H ₂）₂ C ₆ H ₃ O）（7）和W（O）（CHCMe ₂ Ph）（PMe ₂ Ph ）（Me ₂ Pyr）（TPPO）（TPPO = 2,3,5,6-四苯酚酸酯）（8）。顺式同构互补（> 98％顺式同构））聚合物是通过Mo（N-2,6-Me ₂ C ₆ H ₃）（CHCMe ₂ Ph）（OBiphen）（OBiphen = 3,3'-二叔丁基-5,5 '， 6,6'-四甲基-1,1'-联苯-2,2'-二醇酸酯）（5）及其钨类似物W（N-2,6-Me ₂ C ₆ H ₃）（CHCMe ₂ Ph）（OBiphen ）（6）。值得注意的是，这些基于Mo和W的引发剂均未聚合未保护的文斯内酰胺。聚的脱保护（Ñ -TMS文斯内酰胺）和聚（Ñ -Boc文斯内酰胺）与允许的隔离纯三氟乙酸所有-顺 高战术聚（Vince内酰胺）。