Anthracene Photodimer-Derived Chiral Monophosphine Ligands: Preparative Route through Chemical Resolution and Synthetic Application in Asymmetric Allylic Amination

doi:10.6023/cjoc202409013

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (6): 2208-2221.DOI: 10.6023/cjoc202409013 Previous Articles Next Articles

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蒽光二聚体衍生的手性单膦配体: 借助化学拆分的制备路线和不对称烯丙基胺化的合成应用

任天磊^a^,^b, 汪鑫^a^,^b, 丛欢^a^,^b^,^*()

^a 中国科学院理化技术研究所中国科学院光化学转换与功能材料重点实验室北京 100190
^b 中国科学院大学北京 100049

收稿日期:2024-09-12 修回日期:2024-10-31 发布日期:2024-11-20
通讯作者: 丛欢
基金资助:
国家自然科学基金(22071257); 国家自然科学基金(92356307); 中国科学院理化技术研究所所长基金资助项目

Anthracene Photodimer-Derived Chiral Monophosphine Ligands: Preparative Route through Chemical Resolution and Synthetic Application in Asymmetric Allylic Amination

Tianlei Ren^a^,^b, Xin Wang^a^,^b, Huan Cong^a^,^b^,^*()

^a CAS Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190
^b University of Chinese Academy of Sciences, Beijing, 100049

Received:2024-09-12 Revised:2024-10-31 Published:2024-11-20
Contact: Huan Cong
Supported by:
National Natural Science Foundation of China(22071257); National Natural Science Foundation of China(92356307); Technical Institute of Physics and Chemistry Director's Fund, Chinese Academy of Sciences

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Abstract

Anthracene photodimer has a prochiral skeleton, which can be employed as the core structure to construct new chiral ligands. In previous works, the monophosphine ligands derived from optically active anthracene photodimer were prepared through resolution using high performance liquid chromatography, which became a bottleneck for the synthetic scale and cost control. Herein, an inexpensive and operationally friendly route for these ligands is reported, based on chemical resolution. The route features the use of a proline-derived chiral auxiliary that facilitate successful chemical resolution of 1-amino substituted anthracene photodimer. From the resulting optically pure enantiomers, divergent syntheses of a series of anthracene photodimer-derived monophosphine ligands have been achieved. Prepared from the above route, the chiral monophosphine ligand (S_a,S_p)-L1 has been applied to palladium-catalyzed asymmetric allylic amination reactions, which is suitable for a wide range of aniline-type nucleophiles with high yield and enantioselectivity.

Key words: anthracene photodimer, chiral monophosphine ligand, chemical resolution, asymmetric allylic amination, palladium catalysis

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Tianlei Ren, Xin Wang, Huan Cong. Anthracene Photodimer-Derived Chiral Monophosphine Ligands: Preparative Route through Chemical Resolution and Synthetic Application in Asymmetric Allylic Amination[J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2208-2221.

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Fig. & Tab. 6

Scheme 1. (a) Preparation of enantioenriched monophosphine ligands derived from anthracene photodimer through chemical resolution; (b) Application of the monophosphine ligand in palladium-catalyzed asymmetric allylic amination reaction

Scheme 2. Chemical resolution of 1-amino-substituted anthracene photodimer

Figure 1. de values of (Sp,S)-4 and (Rp,S)-4 after resolution determined by HPLC method HPLC condition: OD-H column, n-hexane/i-PrOH (V/V=97/3) as the mobile phase, flow rate=1.0 mL/min.

Scheme 3. Divergent synthesis of chiral monophosphine ligands derived from anthracene photodimer

Table 1. Evaluation of the chiral ligands

Table 2. Substrate scope

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蒽光二聚体衍生的手性单膦配体: 借助化学拆分的制备路线和不对称烯丙基胺化的合成应用

Anthracene Photodimer-Derived Chiral Monophosphine Ligands: Preparative Route through Chemical Resolution and Synthetic Application in Asymmetric Allylic Amination

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Fig. & Tab. 6

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