Synthesis of Conjugated Polyenynes with Alternating Six- and Five-Membered Rings via β-Selective Cascade Metathesis and Metallotropy Polymerization,ACS Macro Letters

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Synthesis of Conjugated Polyenynes with Alternating Six- and Five-Membered Rings via β-Selective Cascade Metathesis and Metallotropy Polymerization
ACS Macro Letters ( IF 5.1 ) Pub Date : 2020-02-19 , DOI: 10.1021/acsmacrolett.9b00986
Cheol Kang ₁ , Jong-Chan Sung ₁ , Kunsoon Kim _{1,

2} , Soon Hyeok Hong ₂ , Tae-Lim Choi ₁

Affiliation

Cascade metathesis and metallotropy (M&M) polymerization, which involves sequential olefin metathesis and metallotropic 1,3-shift reactions specifically from multiyne monomers, is the only method reported so far to prepare conjugated polyenynes via the chain-growth mechanism. Using this method, various conjugated polyenynes containing cyclopentene units in the backbone could be synthesized via exclusive α-addition by using the third-generation Grubbs catalyst. Herein, we demonstrate the complete switch of regioselectivity toward β-addition using a Ru carbene containing a dithiolate ligand, and thus, synthesized unique conjugated polyenynes having alternating cyclohexene and cyclopentene units in the backbone. Furthermore, detailed in situ NMR studies revealed an interesting phenomenon that the adjacent triple bond strongly chelates to the propagating Ru carbene during the polymerization.

中文翻译：

通过β-选择性级联复分解和金属化聚合合成具有交替六元和五元环的共轭多烯

级联复分解和金属化 (M&M) 聚合，包括连续烯烃复分解和金属化 1,3 位移反应，特别是多炔单体，是迄今为止报道的通过链增长机制制备共轭多烯的唯一方法。使用该方法，可以使用第三代 Grubbs 催化剂通过独家 α-加成合成骨架中含有环戊烯单元的各种共轭多烯。在此，我们证明了使用含有二硫醇盐配体的Ru卡宾将区域选择性完全转换为β-加成，从而合成了在主链中具有交替的环己烯和环戊烯单元的独特共轭多烯。此外，

更新日期：2020-02-19

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