可见光催化烷基醇经噻蒽盐的脱羟基(次)膦酰化反应

doi:10.6023/cjoc202505005

有机化学 ›› 2025, Vol. 45 ›› Issue (12): 4468-4480.DOI: 10.6023/cjoc202505005 上一篇下一篇

研究论文

可见光催化烷基醇经噻蒽盐的脱羟基(次)膦酰化反应

张欢^a^,^†, 崔中赫^a^,^†, 朱林^b^,^c^,^*(), 李超忠^a^,^b^,^c

^a 上海科技大学物质科学与技术学院上海 201210
^b 中国科学院上海有机化学研究所先进氮氟材料全国重点实验室先进氮氟材料全国重点实验室上海 200032
^c 南京大学化学化工学院配位化学全国重点实验室配位化学全国重点实验室南京 210093

收稿日期:2025-05-06 修回日期:2025-05-21 发布日期:2025-06-06
通讯作者: 朱林
作者简介:
^† 共同第一作者
基金资助:
南京大学化学化工学院配位化学全国重点实验室开放基金和国家自然科学基金(22193012); 南京大学化学化工学院配位化学全国重点实验室开放基金和国家自然科学基金(22193014); 南京大学化学化工学院配位化学全国重点实验室开放基金和国家自然科学基金(21971253)

Visible-Light-Catalyzed Deoxyphosphonylation and Deoxyphosphinylation of Alkyl Alcohols via Thianthrenium Salts

Huan Zhang^a, Zhonghe Cui^a, Lin Zhu^b^,^c^,^*(), Chaozhong Li^a^,^b^,^c

^a School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210
^b Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
^c State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093

Received:2025-05-06 Revised:2025-05-21 Published:2025-06-06
Contact: Lin Zhu
About author:
†These authors contributed equally to this work
Supported by:
Open Research Fund of State Key Laboratory of Coordination Chemistry, School of Chemistry and Engineering, Nanjing University, and the National Natural Science Foundation of China(22193012); Open Research Fund of State Key Laboratory of Coordination Chemistry, School of Chemistry and Engineering, Nanjing University, and the National Natural Science Foundation of China(22193014); Open Research Fund of State Key Laboratory of Coordination Chemistry, School of Chemistry and Engineering, Nanjing University, and the National Natural Science Foundation of China(21971253)

文章分享

1. 254468S.pdf(1925KB)

摘要/Abstract

发展了一种可见光氧化还原催化下烷基醇经噻蒽盐的脱羟基膦酰化和次膦酰化反应. 该方法条件简单, 无需使用昂贵试剂, 并且作为羟基活化试剂的噻蒽能够回收利用. 与此同时, 这两类反应具有广泛的底物适用范围和良好的官能团兼容性, 并成功应用于一系列复杂生物活性分子的后期修饰, 有望成为烷基膦酸酯和次膦酸酯的实用合成方法.

关键词: 烷基醇, 噻蒽盐, 脱羟基膦酰化, 脱羟基次膦酰化, 自由基

A photoredox-catalyzed system has been developed for the deoxyphosphonylation and deoxyphosphinylation of alkyl alcohols via thianthrenium salts. This methodology features simple reaction conditions, avoids the use of expensive reagents, and enables efficient recovery and reuse of thianthrenium reagent as hydroxyl-activating agent. Notably, both transformations exhibit broad substrate scope and good functional group compatibility, and have been successfully applied to the late-stage modification of various complex bioactive molecules. This protocol represents a promising methodology for practical synthesis of alkylphosphonates and alkylphosphinates.

Key words: alkanol, thianthrenium salt, deoxyphosphonylation, deoxyphosphinylation, radical

引用此文

张欢, 崔中赫, 朱林, 李超忠. 可见光催化烷基醇经噻蒽盐的脱羟基(次)膦酰化反应[J]. 有机化学, 2025, 45(12): 4468-4480.

Huan Zhang, Zhonghe Cui, Lin Zhu, Chaozhong Li. Visible-Light-Catalyzed Deoxyphosphonylation and Deoxyphosphinylation of Alkyl Alcohols via Thianthrenium Salts[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4468-4480.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 5

参考文献 27

[1]	(a) Quin L. D. A Guide to Organophosphorus Chemistry, John Wiley & Sons, Inc., New York, 2000, pp. 351-379.
	(b) Timperley C. M.; Tattersall J. In Organophosphorus (V) Chemistry, Chs. 1, Eds.: Timperley, C. M., Academic Press, London, United Kingdom, 2013, pp. 1-89.
	(c) Yu H.; Yang H.; Shi E.; Tang W. Med. Drug Discovery 2020, 8, 100063. doi: 10.1016/j.medidd.2020.100063
[2]	(a) Engel R. Chem. Rev. 2009, 78, 65. doi: 10.1021/cr60311a005 pmid: 25144792
	(b) Pradere U.; Garnier-Amblard E. C.; Coats S. J.; Amblard F.; Schinazi R. F. Chem. Rev. 2014, 114, 9154. doi: 10.1021/cr5002035 pmid: 25144792
[3]	Kinney W. A.; Abou-Gharbia M.; Garrison D. T.; Schmid J.; Kowal D. M.; Bramlett D. R.; Miller T. L.; Tasse R. P.; Zaleska M. M.; Moyer J. A. J. Med. Chem. 1998, 41, 2236.
[4]	Pampulha M. E.; Ferreira M. A. S. S.; Oliveira A. J. Basic Microbiol. 2007, 47, 325. doi: 10.1002/jobm.v47:4
[5]	Yan M.; Lo J. C.; Edwards J. T.; Baran P. S. J. Am. Chem. Soc. 2016, 138, 12692. doi: 10.1021/jacs.6b08856
[6]	Reich D.; Noble A.; Aggarwal V. K. Angew. Chem., Int. Ed. 2022, 61, e202207063. doi: 10.1002/anie.v61.37
[7]	Ota K.; Nagao K.; Hata D.; Sugiyama H.; Segawa Y.; Tokunoh R.; Seki T.; Miyamoto N.; Sasaki Y.; Ohimiya H. Nat. Commun. 2023, 14, 6856. doi: 10.1038/s41467-023-42639-y
[8]	Lei Z.; Zhang W.; Wu J. ACS Catal. 2023, 13, 16105. doi: 10.1021/acscatal.3c04621
[9]	Ke L.; Tang Y.; Yi H.; Li Y.; Cheng Y.; Liu C.; Lei A. Angew. Chem., Int. Ed. 2015, 54, 6604. doi: 10.1002/anie.v54.22
[10]	Li C.-K.; Tao Z.-K.; Shoberu A.; Zhang W.; Zou J.-P. Org. Lett. 2022, 24, 6083. doi: 10.1021/acs.orglett.2c02454
[11]	Zhou H.; Fan L.-W.; Ren Y.-Q.; Wang L.-L.; Yang C.-C.; Gu Q.-S.; Li Z.-L.; Liu X.-Y. Angew. Chem., Int. Ed. 2023, 62, e202218523. doi: 10.1002/anie.v62.13
[12]	Wang L.-L.; Zhou H.; Cao Y.-X.; Zhang C.; Ren Y.-Q.; Li Z.-L.; Gu Q.-S.; Liu X.-Y. Nat. Synth. 2023, 2, 430. doi: 10.1038/s44160-023-00252-3
[13]	Li H.-H.; Liu Y.; Kramer S. Angew. Chem., Int. Ed. 2025, 64, e202420613. doi: 10.1002/anie.v64.6
[14]	Yin J.; Lin X.; Chai L.; Wang C.-Y.; Zhu L.; Li C. Chem 2023, 9, 1945. doi: 10.1016/j.chempr.2023.03.016
[15]	Pagire S. K.; Shu C.; Reich D.; Noble A.; Aggarwal V. K. J. Am. Chem. Soc. 2023, 145, 18649. doi: 10.1021/jacs.3c06524
[16]	Chai L.; Wang J.; Yang J.; Yin J.; Zhang Z.; Cheng Y.; Zhu L.; Xue X.-S.; Li C. CCS Chem. 2024, 6, 1312. doi: 10.31635/ccschem.023.202303282
[17]	(a) Bissonnette N. B.; Bisballe N.; Tran A. V.; Rossi-Ashton J. A.; MacMillan D. W. C. J. Am. Chem. Soc. 2024, 146, 7942. doi: 10.1021/jacs.4c00557 pmid: 38470101
	(b) Wang J.; Zhang Y.; Zhu L.; Xue X.-S.; Li C. Angew. Chem., Int. Ed. 2024, 63, e202400856. doi: 10.1002/anie.v63.23 pmid: 38470101
	(c) Zhang H.; Cui Z.; Wang J.; Zhu L.; Li C. Org. Chem. Front. 2024, 11, 4502. doi: 10.1039/D4QO00863D pmid: 38470101
	(d) Yuan K.-N.; Xie T.; Wang J.-B.; Wang D.; Shang M. Angew. Chem., Int. Ed. 2025, 64, e202500744. doi: 10.1002/anie.v64.15 pmid: 38470101
[18]	(a) Zhang W.; Luo H.-T.; Yang J.-D. Chem 2023, 9, 2735. doi: 10.1016/j.chempr.2023.09.011
	(b) Tang J.-Y.; Ni J.-X.; Chen Q. Tetrahedron Lett. 2024, 149, 155266. doi: 10.1016/j.tetlet.2024.155266
[19]	(a) Cheng Y.; Zhen J.; Chai L.; Wang J.; Yin J.; Zhu L.; Li C. Angew. Chem., Int. Ed. 2024, 63, e20316764.
	(b) Chai L.; Cheng Y.; Zhu L.; Li C. CCS Chem. 2025, 7, 44. doi: 10.31635/ccschem.024.202404368
[20]	Dong Z.; MacMillan D. W. C. Nature 2021, 598, 451. doi: 10.1038/s41586-021-03920-6
[21]	Stache E. E.; Ertel A. B.; Rovis T.; Doyle A. G. ACS Catal. 2018, 8, 11134. doi: 10.1021/acscatal.8b03592 pmid: 31367474
[22]	Li W.-D.; Wu Y.; Li S.-J.; Jiang Y.-Q.; Li Y.-L.; Lan Y.; Xia J.-B. J. Am. Chem. Soc. 2022, 144, 8551. doi: 10.1021/jacs.1c12463
[23]	Lackner G. L.; Quasdorf K. W.; Overman L. E. J. Am. Chem. Soc. 2013, 135, 15342. doi: 10.1021/ja408971t
[24]	Togo H.; Matsubayashi S.; Yamazaki O.; Yokoyama M. J. Org. Chem. 2000, 65, 2816. pmid: 10808463
[25]	Nawrat C. C.; Jamison C. R.; Slutskyy Y.; MacMillan D. W. C.; Overman L. E. J. Am. Chem. Soc. 2015, 137, 11270. doi: 10.1021/jacs.5b07678
[26]	(a) Chen C.; Wang Z.-J.; Lu H.; Zhao Y.; Shi Z. Nat. Commun. 2021, 12, 4526. doi: 10.1038/s41467-021-24716-2
	(b) Meng H.; Liu M.-S.; Shu W. Chem. Sci. 2022, 13, 13690. doi: 10.1039/D2SC04507A
[27]	Bell A. J.; Ferrante F.; Hall S. E.; Mikhalilov V.; Mitchell D.; Timperley C. M.; Watts P.; Williams N. Int. J. Mass Spectrom. 2008, 269, 46. doi: 10.1016/j.ijms.2007.09.004

Entry	Variation from optimal conditions	Yield^b/%
1	Without Et₃N	39
2	DMA as solvent, without Et₃N	24
3	MeCN as solvent, without Et₃N	Trace
4	DCE as solvent, without Et₃N	N.D.^c
5	EtOAc as solvent, without Et₃N	N.D.
6	DABCO instead of Et₃N	N.D.
7	Quinuclidine instead of Et₃N	10
8	DIPEA instead of Et₃N	61
9	None	81 (74^d)
10	1.0 equiv. Et₃N	59
11	3.0 equiv. Et₃N	82
12	4CzIPN instead of 4DPAIPN	73
13	fac-Ir(ppy)₃instead of 4DPAIPN	25
14	3DPA2FBN instead of 4DPAIPN	33
15	P-2 instead of P-1	35
16	P(OMe)₃ instead of P-1	25^e
17	1.0 equiv. P-1	65
18	3.0 equiv. P-1	83
19	390~410 nm blue LEDs	53
20	Without photocatalyst	N.D.
21	In the dark	N.D.

Entry	Variation from optimal conditions	Yield^b/%
1	Without Et₃N	39
2	DMA as solvent, without Et₃N	24
3	MeCN as solvent, without Et₃N	Trace
4	DCE as solvent, without Et₃N	N.D.^c
5	EtOAc as solvent, without Et₃N	N.D.
6	DABCO instead of Et₃N	N.D.
7	Quinuclidine instead of Et₃N	10
8	DIPEA instead of Et₃N	61
9	None	81 (74^d)
10	1.0 equiv. Et₃N	59
11	3.0 equiv. Et₃N	82
12	4CzIPN instead of 4DPAIPN	73
13	fac-Ir(ppy)₃instead of 4DPAIPN	25
14	3DPA2FBN instead of 4DPAIPN	33
15	P-2 instead of P-1	35
16	P(OMe)₃ instead of P-1	25^e
17	1.0 equiv. P-1	65
18	3.0 equiv. P-1	83
19	390~410 nm blue LEDs	53
20	Without photocatalyst	N.D.
21	In the dark	N.D.

可见光催化烷基醇经噻蒽盐的脱羟基(次)膦酰化反应

Visible-Light-Catalyzed Deoxyphosphonylation and Deoxyphosphinylation of Alkyl Alcohols via Thianthrenium Salts

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 5

参考文献 27

相关文章 15

编辑推荐

相关统计

本文评价

[1]	李欢乐, 潘其, 娄绍杰, 毛羊杰, 许丹倩. 基于氢原子迁移(HAT)过程的胺类化合物选择性C—H键转化反应研究进展[J]. 有机化学, 2025, 45(9): 3213-3243.
[2]	任博文, 方通昌, 刘超. 可见光诱导双硼化合成烷基偕二硼酸酯^★[J]. 有机化学, 2025, 45(9): 3343-3350.
[3]	张斌斌, 刘露娜, 竺杨彬, 邹东. 自由基介导的硝基芳烃活化反应研究进展[J]. 有机化学, 2025, 45(8): 2698-2725.
[4]	高根伟, 李震, 李炎, 陆熹. 光/镍协同催化C(sp²)—C(sp³)键构建研究进展[J]. 有机化学, 2025, 45(6): 1905-1919.
[5]	姚嫣, 付年凯. 光电化学金属催化研究进展[J]. 有机化学, 2025, 45(6): 1819-1837.
[6]	谭永波, 舒洪波, 黄华文. 光诱导N-芳基丙烯酰胺参与的吲哚酮合成研究进展[J]. 有机化学, 2025, 45(6): 2086-2108.
[7]	李慧, 阿布力米提•阿布都卡德尔, 周磊. 可见光条件下N-苄基苯并三氮唑自由基脱氮气开环合成6-取代菲啶[J]. 有机化学, 2025, 45(5): 1770-1777.
[8]	李顺曦, 游力栩, 李玉龙, 舒伟. 光介导氨及其等价体参与的碳氮成键反应研究进展[J]. 有机化学, 2025, 45(5): 1460-1477.
[9]	陈旭欣, 张丹丹, 龙鸿新, 刘国凯. 无需光敏剂光诱导炔丙酸酯自由基二氟甲基化合成3-二氟甲基香豆素[J]. 有机化学, 2025, 45(5): 1739-1746.
[10]	郭仕勋, 王卫, 张永强. 三线态能量转移促进的自由基链式烯烃氢芳基化反应研究[J]. 有机化学, 2025, 45(5): 1716-1728.
[11]	李晨, 焦毅, 施笑然, 杨毅强, 俞寿云. 光氧化还原催化的C-糖基化反应[J]. 有机化学, 2025, 45(5): 1423-1459.
[12]	谭芳芳, 史孟欣, 张文敏, 李洋. 光催化生物质相关转化[J]. 有机化学, 2025, 45(5): 1523-1547.
[13]	蒋晨阳, 尹艳丽, 江智勇. 光酶催化不对称自由基加成反应研究进展[J]. 有机化学, 2025, 45(5): 1614-1633.
[14]	吴昊岩, 赫明月, 马军安, 张发光. 三芳胺在光催化反应中的研究进展[J]. 有机化学, 2025, 45(5): 1634-1643.
[15]	范玉兰, 邹小颖, 朱小青, 郑绿茵, 郭维. N-邻位C(sp³)—H键官能团化合成含氮杂环化合物研究进展[J]. 有机化学, 2025, 45(4): 1047-1096.