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化学学报
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化学学报 ›› 2026, Vol. 84 ›› Issue (9): 1412-1417.DOI: 10.6023/A26080277 上一篇    下一篇

研究通讯

SPSiOL衍生膦-膦氧配体SPSiP(O)的合成及应用

曾晓萱a, 吴奕晨a,*(), 王鹏a,b,*()   

  1. a 中国科学院上海有机化学研究所 金属有机化学全国重点实验室和沪港化学合成联合实验室 金属有机化学全国重点实验室和沪港化学合成联合实验室 上海 200032
    b 国科大杭州高等研究院 化学与材料科学学院 化学与材料科学学院 杭州 310024
  • 投稿日期:2026-08-03 发布日期:2026-09-21
  • 通讯作者: 吴奕晨, 王鹏
  • 基金资助:
    国家重点研发计划(2023YFF0723900); 中国科学院战略性先导科技专项(XDB1180000); 中国科学院战略性先导科技专项(XDB0610000); 国家自然科学基金(22371293)

Synthesis and Application of SPSiP(O)s: a Class of SPSiOL-Derived Bisphosphine Monoxide Ligands

Xiao-Xuan Zenga, Yichen Wua,*(), Peng Wanga,b,*()   

  1. a State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
    b School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China
  • Received:2026-08-03 Published:2026-09-21
  • Contact: Yichen Wu, Peng Wang
  • Supported by:
    The National Key R&D Program of China(2023YFF0723900); The Strategic Priority Research Program of the Chinese Academy of Sciences(XDB1180000); The Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000); The National Natural Science Foundation of China(22371293)

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本工作报道了一类手性螺二氢苯并噻咯二酚(SPSiOL)衍生的膦-膦氧配体[SPSiP(O)]的合成和应用. 从SPSiOL-衍生的双三氟甲磺酸酯出发, 该类配体可以通过钯催化膦氧偶联、膦氧还原及进一步膦氧偶联反应高效制备. 利用该类型配体, 首次实现了前手性联苯二溴化物不对称Heck反应, 通过去对称化策略快速构建轴手性联苯类化合物, 最高可以取得67%的产率和82% ee. 该反应的实现初步验证了SPSiP(O)配体在不对称催化反应中的应用潜力.

关键词: 膦-膦氧配体, SPSiOL, SPSiP(O), Heck反应, 不对称催化

Transition metal catalyzed asymmetric reactions represent one of the most important synthetic strategies for the access of chiral compounds. Throughout the development of asymmetric catalysis, chiral ligands have played a vital role, not only in modulating catalytic activity but also in controlling stereochemical induction. Among numerous chiral ligands, chiral bisphosphine monoxide ligand has attracted increasing attention owing to their unique hemilabile coordination properties, which can facilitate efficient transition metal catalysis under mild reaction conditions. Herein, we report the synthesis and application of SPSiOL-derived bisphosphine monoxide ligands SPSiP(O)s. These ligands can be readily prepared in three steps through a Pd-catalyzed cross-coupling of (S)-SPSiOL triflate with diarylphosphine oxide, reduction of the phosphine oxide moiety, and a subsequent Pd-catalyzed coupling reaction with another diarylphosphine oxide, enabling the modular synthesis of SPSiP(O) ligands with diverse electronic and steric variations on both the phosphine and phosphine oxide units. The catalytic potential of SPSiP(O)s was evaluated in a Pd-catalyzed asymmetric Heck-type reaction between 1-aryl-2,6-dibromides and alkenes. After optimization, axially chiral biaryl products were obtained in up to 67% yield and 82% ee using Pd(dba)2/SPSiP(O). Ligand screening revealed that SPSiP(O) ligands were uniquely effective, with both the electronic and steric properties of the phosphine moiety significantly influencing catalytic efficiency and enantioselectivity. The substrate scope of this asymmetric Heck reaction was subsequently examined, demonstrating broad functional group tolerance and the general applicability. Notably, this reaction represents the first asymmetric Heck desymmetrization of prochiral biphenyl dibromides for the synthesis of axially chiral biphenyl frameworks, highlighting the potential of SPSiP(O)s as versatile ligands for asymmetric catalysis.

Key words: bisphosphine monoxide ligand, SPSiOL, SPSiP(O), Heck reaction, asymmetric catalysis