Hydroxy-telechelic polyalkenamers have long been synthesized using ring-opening metathesis polymerization (ROMP) in the presence of an acyclic olefin chain-transfer agent (CTA); however, this route typically requires protected diols in the CTA due to the challenge of alcohol-mediated degradation of ruthenium metathesis catalysts that can not only deactivate the catalysts, but also compromise the CTA. We demonstrate the synthesis and implementation of a new hydroxyl-containing CTA in which extended methylene spacers isolate the olefin and alcohol moieties to mitigate decomposition pathways. This CTA enabled the direct ROMP synthesis of hydroxy-telechelic polycyclooctene with controlled chain lengths dictated by the initial ratio of monomer to CTA. The elimination of protection/deprotection steps resulted in improved atom economy. Subsequent hydrogenation of the backbone olefins was performed by a one-pot, catalytic approach employing the ruthenium complex used for the initial ROMP. The resultant approach is a streamlined, atom-economic, and low-waste route to hydroxy-telechelic linear polyethylene that uses a green solvent, succeeds with miniscule quantities of catalyst (0.005 mol %), and requires no additional purification steps.

中文翻译：

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羟基-遥爪线性聚乙烯的串联ROMP/氢化方法

长期以来，羟基遥爪多链烯单体一直是在无环烯烃链转移剂 (CTA) 存在下使用开环复分解聚合 (ROMP) 合成的；然而，由于酒精介导的钌复分解催化剂降解的挑战，该路线通常需要在 CTA 中保护二醇，这不仅会使催化剂失活，还会损害 CTA。我们展示了一种新的含羟基 CTA 的合成和实施，其中扩展的亚甲基间隔物分离烯烃和醇部分以减轻分解途径。这种 CTA 使羟基-遥爪聚环辛烯的直接 ROMP 合成成为可能，其链长由单体与 CTA 的初始比例决定。消除保护/去保护步骤导致原子经济性提高。骨架烯烃的后续氢化通过一锅催化方法进行，该方法使用用于初始ROMP的钌络合物。由此产生的方法是一种使用绿色溶剂、使用微量催化剂 (0.005 mol%) 且无需额外纯化步骤即可获得羟基遥爪线性聚乙烯的流线型、原子经济且低浪费的路线。