Tandem asymmetric dearomatized functionalization reaction of phenols with Evans-ynamides enabled by divergent electrophiles

被引：1

作者：

Zhang, Ying-Qi ^{[1
,2
]}

Qian, Gan-Lu ^{[3
]}

Liu, Yun ^{[1
,2
]}

Li, Jia-Hui ^{[1
,2
]}

Hong, Xin ^{[3
]}

Xu, Zhou ^{[4
]}

Zhou, Bo ^{[1
,2
]}

Ye, Long-Wu ^{[1
,2
,5
,6
]}

机构：

[1] Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Key Lab Chem Biol Fujian Prov, Xiamen 361005, Peoples R China

[2] Xiamen Univ, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China

[3] Zhejiang Univ, Ctr Chem Frontier Technol, Dept Chem, State Key Lab Clean Energy Utilizat, Hangzhou 310027, Peoples R China

[4] Xuzhou Med Univ, Sch Pharm, Jiangsu Key Lab New Drug Res & Clin Pharm, Xuzhou 221004, Peoples R China

[5] Nankai Univ, State Key Lab Elemento Organ Chem, Tianjin 300071, Peoples R China

[6] Chinese Acad Sci, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China

来源：

SCIENCE CHINA-CHEMISTRY | 2025年 / 68卷 / 02期

基金：

国家重点研发计划; 中国国家自然科学基金;

关键词：

alkynes; cyclization; dearomatization; Evans chiral auxiliary; spirocycles; QUATERNARY STEREOGENIC CENTERS; ENANTIOSELECTIVE SYNTHESIS; CHIRAL AUXILIARIES; KINETIC RESOLUTION; ALDOL PRODUCTS; UNIQUE; CATALYSIS; ALKENES; HALOFUNCTIONALIZATION; CYCLOADDITIONS;

D O I：

10.1007/s11426-024-2211-y

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Herein, we disclose a highly regio-/chemoselective tandem asymmetric dearomatized halofunctionalization reaction of phenol-tethered ynamides with diverse electrophilic halogenation sources in a catalyst-free manner for the practical and rapid assembly of a series of halogenated spirocyclic enones. Besides, the related dearomatized selenation and protonation are also achieved, affording the corresponding selenated and protonated spirocycles in high efficiency. Moreover, the enantioselectivities of these products can be perfectly induced by Evans auxiliaries (99% ees). Significantly, this protocol not only represents the first tandem asymmetric halofunctionalization reaction of phenol derivatives, but also constitutes the first asymmetric halogenation/selenation of ynamides. Theoretical calculations indicate a remote induction model of Evans chiral auxiliary-attached keteniminium.

引用

页码：649 / 660

页数：12

共 4 条

[1] Tandem asymmetric dearomatized functionalization reaction of phenols with Evans-ynamides enabled by divergent electrophiles
YingQi Zhang
GanLu Qian
Yun Liu
JiaHui Li
Xin Hong
Zhou Xu
Bo Zhou
LongWu Ye
Science China(Chemistry), 2025, 68 (02) : 649 - 660
[2] Organocatalytic asymmetric tandem α-functionalization/1,3-proton shift reaction of benzylidene succinimides with β-trifluoromethyl enones
Zhang, Xia-Yan
You, Yong
Wang, Zhen-Hua
Zhao, Jian-Qiang
Yuan, Wei-Cheng
CHEMICAL COMMUNICATIONS, 2020, 56 (87) : 13449 - 13452
[3] Catalytic asymmetric multiple dearomatizations of phenols enabled by a cascade 1,8-addition and Diels-Alder reaction
Liu, Xihong
Zhang, Jingying
Bai, Lutao
Wang, Linqing
Yang, Dongxu
Wang, Rui
CHEMICAL SCIENCE, 2020, 11 (03) : 671 - 676
[4] Sadphos-Enabled Asymmetric Tandem Denitrogenative Heck/Tsuji-Trost Reaction of Benzotriazoles with 1,3-Dienes
Li, Yunshan
Tang, Yefeng
CHINESE JOURNAL OF ORGANIC CHEMISTRY, 2021, 41 (11) : 4512 - 4514

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