无过渡金属参与的偕二氟环丙烷双脱氟烷氧基化合成环丙酮缩酮

doi:10.6023/cjoc202406020

研究论文

无过渡金属参与的偕二氟环丙烷双脱氟烷氧基化合成环丙酮缩酮

车琳^a, 江忠涛^b, 杨慧^b, 胡芳东^a,*, 夏莹^b,*

^a临沂大学化学化工学院山东临沂 276000;
^b四川大学华西公共卫生学院/华西第四医院生物治疗全国重点实验室四川成都 610041

收稿日期:2024-06-14 修回日期:2024-07-28
基金资助:
国家自然科学基金(No. 22371189, 22001180, 21801109)、青年千人计划(No. 15-YINGXIA)和山东省自然科学基金(No. ZR2018BB019)资助项目.

Transition-Metal Free Synthesis of Cyclopropanone Ketals via Double Defluorinative Alkoxylation of gem-Difluorinated Cyclopropanes

Che Lin^a, Jiang Zhong-Tao^b, Yang Hui^b, Hu Fangdong^a,*, Xia Ying^b,*

^aSchool of Chemistry and Chemical Engineering, Linyi University, Linyi, Shandong 276000;
^bWest China School of Public Health and West China Fourth Hospital, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu, Sichuan 610041

Received:2024-06-14 Revised:2024-07-28
Contact: *E-mail: hufangdong@lyu.edu.cn; xiayingscu@scu.edu.cn
Supported by:
National Natural Science Foundation of China (No. 22371189, 22001180, 21801109), Thousand Young Talents Program (No. 15-YINGXIA) and the Natural Science Foundation of Shandong Province (No. ZR2018BB019).

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摘要/Abstract

在不发生高张力C-C键断裂的情况下实现偕二氟环丙烷中C-F键的转化是一个棘手的挑战。在无过渡金属参与的碱性条件下,我们发展了通过偕二氟环丙烷的双脱氟化合成环丙酮缩酮的第一个实例。多种偕二氟环丙烷和醇可用于目前的反应,以高收率合成相应的产物。在机理研究的基础上说明了该反应是通过消除加成而不是直接取代进行的。这不仅为环丙酮缩酮的合成提供了一种新的策略,而且为偕二氟环丙烷的非开环C-F键转化提供了一种新的范例。

关键词: 偕二氟环丙烷, 脱氟化, 烷氧基化, 环丙酮缩酮, 消除与加成

The C-F bond transformation of gem-difluorinated cyclopropanes without cleavage of the highly strained C-C bond is an intractable challenge. We herein develope the first example on the synthesis of cyclopropanone ketals via double defluorination of gem-difluorinated cyclopropanes under transition-metal free and basic conditions. A broad range of gem-difluorinated cyclopropanes and alcohols are amenable in present reaction to permit the synthesis of corresponding products in high yields. The reaction is elucidated to proceed via elimination and addition other than direct substitution based on the mechanistic studies. This transformation not only provides a new strategy for the construction of cyclopropanone ketals, but also reveals a new paradigm on C-F bond transformation without ring-opening of gem-difluorinated cyclopropanes.

Key words: gem-difluorinated cyclopropanes, defluorination, alkoxylation, cyclopropanone ketals, elimination and addition

引用此文

车琳, 江忠涛, 杨慧, 胡芳东, 夏莹. 无过渡金属参与的偕二氟环丙烷双脱氟烷氧基化合成环丙酮缩酮[J]. 有机化学, doi: 10.6023/cjoc202406020.

Che Lin, Jiang Zhong-Tao, Yang Hui, Hu Fangdong, Xia Ying. Transition-Metal Free Synthesis of Cyclopropanone Ketals via Double Defluorinative Alkoxylation of gem-Difluorinated Cyclopropanes[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202406020.

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参考文献

[1](a) Jiang Z.-T.; Zeng Y.; Xia Y. Synlett2021, 32, 1675.
(b) Lv L.; Qian H.; Li Z. ChemCatChem2022, 14, e202200890
(b) Zhu Y.; Zeng Y.; Jiang Z.-T.; Xia Y. Synlett2023, 34, 1.
(c) Zeng Y.; Jiang Z.-T.; Xia Y. Chem. Commun.2024, 60, 3764.
[2]Dolbier, W. R.; Battiste, M. A.Chem. Rev. 2003, 103, 1071.
[3](a) Zeng Y.; Xia, Y. Angew. Chem. Int. Ed.2023, 62, e202307129.
(b) Wu X.; Song X.; Xia Y. Adv. Sci.2024, 11, 2401243.
[4]Banik S. M.; Mennie K. M.; Jacobsen, E. N. J. Am. Chem. Soc.2017, 139, 9152.
[5](a) Liu H.; Li Y.; Wang D.-X.; Sun M.-M.; Feng C. Org. Lett.2020, 22, 8681.
(b) Zhao Y.-R.; Ma Z.-Y.; Liu L.; Guo P.; Duan X.-H.; Hu, M. J. Org. Chem.2023, 88, 3787.
[6](a) Goto T.; Kawasaki-Takasuka T.; Yamazaki, T. J. Org. Chem.2019, 84, 9509.
(b) Liu H.; Tian L.; Wang H.; Li Z.-Q.; Zhang C.; Xue F.; Feng C. Chem. Sci.2022, 13, 2686.
[7]For linear selectivity:
(a) Xu J.; Ahmed E.-A.; Xiao B.; Lu Q.-Q.; Wang Y.-L.; Yu C.-G.; Fu, Y. Angew. Chem. Int. Ed.2015, 54, 8231.
(b) Ahmed E.-A. M. A.; Suliman A. M. Y.; Gong T.-J.; Fu Y. Org. Lett.2019, 21, 5645.
(c) Ahmed E.-A. M. A.; Suliman A. M. Y.; Gong T.-J.; Fu Y. Org. Lett.2020, 22, 1414.
(d) Zhou P.-X.; Yang X.; Wang J.; Ge C.; Feng W.; Liang Y.-M.; Zhang Y. Org. Lett.2021, 23, 4920.
(e) Suliman A. M. Y.; Ahmed E.-A. M. A.; Gong T.-J.; Fu Y. Org. Lett.2021, 23, 3259.
(f) Suliman A. M. Y.; Ahmed E.-A. M. A.; Gong T.-J.; Fu Y. Chem. Commun.2021, 57, 6400.
(g) Xiong B.; Chen X.; Liu J.; Zhang X.; Xia Y.; Lian Z. ACS Catal.2021, 11, 11960.
(h) Yuan, W.; Li, X.; Qi, Z.; Li, X.Org. Lett. 2022, 24, 2093.
(i) Ahmed E.-A. M. A.; Zhang H.; Cao W.-G.; Gong T.-J. Org. Lett.2023, 25, 9020.
(j) Sun J.; Ye H.; Sun F.; Pan Y.-Y.; Zhu X.-W.; Wu X.-X. Org. Lett.2023, 25, 5220.
(k) Li D.; Shen C.; Si Z.; Liu, L. Angew. Chem. Int. Ed.2023, 62, e202310283.
(l) Qian H.; Nguyen H. D.; Lv L.; Chen S.; Li, Z. Angew. Chem. Int. Ed.2023, 62, e202303271.
(m) Liang Z.; Ye H.; Zhang H.; Jiang G.; Wu, X. Chin. J. Org. Chem.2023, 43, 1483 (in Chinese).
(梁志鹏, 叶浩, 张海滨, 姜国民, 吴新星, 有机化学, 2023, 43, 1483.)
(n) Qian H.; Cheng Z. P.; Luo Y.; Lv L.; Chen S.; Li, Z. J. Am. Chem. Soc.2024, 146, 24.
(o) Yan Y.; Lu W.; Qian H.; Lv L.; Li, Z. Chin. J. Org. Chem.2024, 44, 1630 (in Chinese).
(晏宇轩, 陆晚晴, 钱慧俊, 吕雷阳, 李志平, 有机化学, 2024, 44, 1630.
(p) Su Z.; Tan B.; He H.; Chen K.; Chen S.; Lei H.; Chen T.-G.; Ni S.-F.; Li, Z. Angew. Chem. Int. Ed.2024, 63, e202402038.
(q) Su Z.; Tan B.; Li Z.; Huang H.; Zhang Y. Org. Lett.2024, 26, 5375.
[8]For branched selectivity:
(a) Lv L.; Li, C.-J. Angew. Chem. Int. Ed.2021, 60, 13098.
(b) Lv L.; Qian H.; Ma Y.; Huang S.; Yan X.; Li Z. Chem. Sci.2021, 12, 15511.
(c) Lv L.; Qian H.; Crowell A. B.; Chen S.; Li Z. ACS Catal.2022, 12, 6495.
(d) Wu L.; Wang M.; Liang Y.; Shi, Z. Chin. J. Chem.2022, 40, 2345.
[9](a) Jiang Z.-T.; Huang J.; Zeng Y.; Hu F.; Xia, Y. Angew. Chem. Int. Ed.2021, 60, 10626.
(b) Zeng Y.; Gao H.; Zhu Y.; Jiang Z.-T.; Lu G.; Xia Y. ACS Catal.2022, 12, 8857.
(c) Zeng Y.; Yang H.; Du J.; Huang Q.; Huang G.; Xia Y. Chem. Sci.2022, 13, 12419.
(d) Yang H.; Zeng Y.; Song X.; Che L.; Jiang Z.-T.; Lu G.; Xia, Y. Angew. Chem. Int. Ed.2024, 63, e202403602.
(e) Zeng Y.; Gao H.; Jiang Z.-T.; Zhu Y.; Chen J.; Zhang H.; Lu G.; Xia Y. Nat. Commun.2024, 15, 4317.
[10](a) Ai Y.; Yang H.; Duan C.; Li X.; Yu S. Org. Lett.2022, 24, 5051.
(b) Zhao B.; Pan Z.; Pan J.; Deng H.; Bu X.; Ma M.; Xue F. Green Chem.2023, 25, 3095.
(c) Qi S.; Hua,Y.; Pan L.; Yang J.; Zhang, J. Chin. J. Chem.2024, 42, 823.
[11]Wu T.-S.; Hao,Y.-J.; Cai Z.-J.; Ji, S.-J. Org. Chem. Front.2024, 11, 1057.
[12]Jiang Z.-T.; Chen Z.; Xia, Y. Angew. Chem. Int. Ed.2024, 63, e202319647.
[13](a) Amii, H.; Uneyama, K.Chem. Rev. 2009, 109, 2119.
(b) Ahrens T.; Kohlmann J.; Ahrens M.; Braun T. Chem. Rev.2015, 115, 931.
(c) Das A.; Chatani N. ACS Catal.2021, 11, 12915.
(d) Ge, D.; Chu, X.-Q.Org. Chem. Front. 2022, 9, 2013.
(e) Hooker L. V.; Bandar, J. S. Angew. Chem. Int. Ed.2023, 62, e202308880.
[14]Aksenov V. S.; Terent'eva, G. A. Russ Chem. Bull.1978, 27, 1168.
[15]To T. A.; Nguyen, T. V. Angew. Chem. Int. Ed.2024, 63, e202317003.
[16]Reyne F.; Waegell B.; Brun, P. Bull. Chem. Soc. Jpn1995, 68, 1162.