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<p>Axially chiral phosphines are a class of extremely important ligands in asymmetric catalysis. Herein, an unprecedented copper (I)-catalyzed asymmetric S<sub>N</sub>Ar reaction with HP(S)R<sub>2</sub> is uncovered, which delivers a series of axially chiral phosphine derivatives in high yields with excellent enantioselectivity. Furthermore, the diastereoselective reaction with the kinetic resolution of racemic HP(S)ArR proceeds smoothly, providing the products with moderate diastereoselectivity and excellent enantioselectivity. Control experiments indicate that HP(S)Ph<sub>2</sub> is much more active than HPPh<sub>2</sub> and HP(O)Ph<sub>2</sub> as the pronucleophile in the present reaction. It is found that the S<sub>N</sub>Ar reaction (the first S<sub>N</sub>Ar) proceeds in a desymmetric manner, providing the desired chiral products while a continued S<sub>N</sub>Ar reaction (the second S<sub>N</sub>Ar) slightly occurs in a kinetic resolution manner in the present catalytic system, which enhances the ee of the desired chiral products. DFT calculations support a concerted reaction pathway rather than a step-wise mechanism. Finally, axially chiral olefin-phosphines produced by the present method work as suitable ligands in Pd-catalyzed asymmetric allylic substitution with <i>C</i>-, <i>N</i>-, and <i>O</i>-nucleophiles and Rh-catalyzed asymmetric addition of arylboronic acid to benzil.</p>

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Synthesis of chiral phosphine derivatives through a copper(I)-catalyzed desymmetric SNAr reaction

  • 期刊论文

  • 发表日期：

    2025年1月3日

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  • Shuai Zhang,
  • Pei-Zhi Liu,
  • Yan-Bo Li,
  • Qi Zhang,
  • Jun-Zhao Xiao,
  • Yi-Fan Wang,
  • Tian-Yu Wei,
  • Jia-Wei Jiang,
  • Ye Wang,
  • Qian Peng,
  • Liang Yin

摘要

Axially chiral phosphines are a class of extremely important ligands in asymmetric catalysis. Herein, an unprecedented copper (I)-catalyzed asymmetric SNAr reaction with HP(S)R2 is uncovered, which delivers a series of axially chiral phosphine derivatives in high yields with excellent enantioselectivity. Furthermore, the diastereoselective reaction with the kinetic resolution of racemic HP(S)ArR proceeds smoothly, providing the products with moderate diastereoselectivity and excellent enantioselectivity. Control experiments indicate that HP(S)Ph2 is much more active than HPPh2 and HP(O)Ph2 as the pronucleophile in the present reaction. It is found that the SNAr reaction (the first SNAr) proceeds in a desymmetric manner, providing the desired chiral products while a continued SNAr reaction (the second SNAr) slightly occurs in a kinetic resolution manner in the present catalytic system, which enhances the ee of the desired chiral products. DFT calculations support a concerted reaction pathway rather than a step-wise mechanism. Finally, axially chiral olefin-phosphines produced by the present method work as suitable ligands in Pd-catalyzed asymmetric allylic substitution with C-, N-, and O-nucleophiles and Rh-catalyzed asymmetric addition of arylboronic acid to benzil.