Stereoconvergent Synthesis of Z ‐1,3‐Disubstituted‐1,3‐Dienes by Uphill Photocatalysis
Stereoconvergent Synthesis of Z ‐1,3‐Disubstituted‐1,3‐Dienes by Uphill Photocatalysis
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Uphill光催化立体会聚合成Z-1,3-双取代-1,3-二烯
DOI：
10.1002/chem.202202635
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Wild, Thérèse
中科院分区：
文献类型：
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作者：
Diver, Steven T.;Glickert, Elise;Rohde, Jr., Laurence N.;Wild, Thérèse
以Ru（bpy）3[PF 6] 2为催化剂，在蓝光LED灯下，通过双金属催化剂将1-芳基-1，3-二烯异构化为乙二烯。Z-异构体的富集被认为是通过从光催化剂到立体异构体混合物的选择性三重态能量转移而发生的。1，3-二烯起始材料容易通过催化烯-炔复分解（EYM）制备。为了直接获得1，3-二烯Z-立体异构体，开发了一锅法。研究了额外的1，3-二烯的异构化和Z-富集。cross EYM与cross的组合允许Z-1，3-二烯的立体会聚合成。
A variety of 1‐aryl‐1,3‐dienes were isomerized fromEtoZisomers by photocatalysis using Ru(bpy)3[PF6]2and blue LED light. Enrichment of theZ‐isomer is thought to occur by selective triplet energy transfer from the photocatalyst to the stereoisomeric mixture. The 1,3‐diene starting materials are easily made by catalytic ene‐yne metathesis (EYM). To access 1,3‐dieneZ‐stereoisomers directly, a one pot procedure was developed. Additional 1,3‐dienes were investigated for both isomerization andZ‐enrichment. The combination of cross EYM with photocatalysis allows for the stereoconvergent synthesis ofZ‐1,3‐dienes.