We present a stereo-selective preparation of multi-substituted dienes and eneynes by sequential hydroarylation of internal alkynes via five-membered rhodacycle and olefinic C–H functionalization, including alkenylation, alkynylation and allylation through seven-membered endo-cyclopalladation, both enabled by the N,N-bidentate chelation assistance of pyrazinamide or picolinamide. The robustness and generality of the protocol have been demonstrated by the smooth conversion of a wide range of benzyl amides to afford up to 92% yields with E/Z ratio selectivity up to >99/1, as well as a successful gram-scaled synthesis. Further chemical derivations and photophysical properties of products were also examined.

中文翻译：

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通过顺序加氢芳基化和烯属 C-H 官能化立体选择性合成复杂二烯和烯炔


我们提出了一种多取代二烯和烯炔的立体选择性制备方法，通过五元铑环和烯属 C-H 官能化对内部炔烃进行连续氢芳基化，包括通过七元内环钯化进行烯基化、炔基化和烯基化，这两种方法均由吡嗪酰胺或吡啶甲酰胺的 N,N-二齿螯合辅助。该方案的稳健性和通用性已通过多种苄基酰胺的顺利转化得到证明，产率高达 92%，E/Z 比率选择性高达 >99/1，以及成功的克级合成。还检查了产品的进一步化学衍生和光物理性质。