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<p>Olefins are fundamental functional groups and of substantial commercial importance across a broad range of value-added chemicals. Their production from biomass-derived alcohols remains a longstanding goal, while the selective synthesis of trisubstituted olefins presents a formidable challenge that demands precise catalytic control to suppress undesired product formation. Herein, we demonstrate sequential cross-coupling/isomerization and cross-coupling/dehydrogenation of two different alcohols leading to stereoselective synthesis of trisubstituted olefins (27 examples; <i>E</i>/<i>Z</i> up to 98:2) and 1,3-dienes (23 examples; <i>E</i>/Z &gt; 20:1) using a commercially available nickel catalyst enabled by ligand control. Late-stage functionalization using <i>DL</i>-galactose, <i>α</i>-tocopherol and post-product modification to a tamoxifen analogue and polyaromatic hydrocarbon highlight the significance of our developed method. Preliminary mechanistic studies indicate that alcohol dehydrogenation to the corresponding aldehyde is the rate-determining step (<i>P</i><sub>H</sub>/<i>P</i><sub>D</sub> = 4.3). Detailed mechanistic studies and deuterium labelling experiments support an underlying DCR (dehydrogenation-condensation-rehydrogenation) approach, followed by stereo-selective isomerization or dehydrogenation enabled by nickel.</p>

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Modular synthesis of trisubstituted olefins and 1,3-dienes from renewable alcohols via ligand-enabled nickel catalysis

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年6月30日

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  • Adrija Ghosh,
  • Purushotam,
  • Chao-Jun Li,
  • Debasis Banerjee

摘要

Olefins are fundamental functional groups and of substantial commercial importance across a broad range of value-added chemicals. Their production from biomass-derived alcohols remains a longstanding goal, while the selective synthesis of trisubstituted olefins presents a formidable challenge that demands precise catalytic control to suppress undesired product formation. Herein, we demonstrate sequential cross-coupling/isomerization and cross-coupling/dehydrogenation of two different alcohols leading to stereoselective synthesis of trisubstituted olefins (27 examples; E/Z up to 98:2) and 1,3-dienes (23 examples; E/Z > 20:1) using a commercially available nickel catalyst enabled by ligand control. Late-stage functionalization using DL-galactose, α-tocopherol and post-product modification to a tamoxifen analogue and polyaromatic hydrocarbon highlight the significance of our developed method. Preliminary mechanistic studies indicate that alcohol dehydrogenation to the corresponding aldehyde is the rate-determining step (PH/PD = 4.3). Detailed mechanistic studies and deuterium labelling experiments support an underlying DCR (dehydrogenation-condensation-rehydrogenation) approach, followed by stereo-selective isomerization or dehydrogenation enabled by nickel.