可见光促进的含色氨酸寡肽与YlideFluor试剂的直接三氟甲基化反应研究

doi:10.6023/cjoc202209018

有机化学 ›› 2023, Vol. 43 ›› Issue (4): 1517-1524.DOI: 10.6023/cjoc202209018 上一篇下一篇

所属专题：有机氟化学虚拟合辑

研究论文

可见光促进的含色氨酸寡肽与YlideFluor试剂的直接三氟甲基化反应研究

刘静^a, 郝健^a^,^*(), 沈其龙^b^,^*()

a 上海大学化学系上海 200444
b 中国科学院上海有机化学研究所有机氟化学重点实验室上海 200032

收稿日期:2022-09-14 修回日期:2022-11-14 发布日期:2022-11-21
通讯作者: 郝健, 沈其龙
基金资助:
国家重点研发计划(2021YFF0701700)

Visible-Light-Promoted Direct Trifluoromethylation of Tryptophan-Containing Oligapeptides with YlideFluor

Jing Liu^a, Jian Hao^a(), Qilong Shen^b()

a Department of Chemistry, Shanghai University, Shanghai 200444
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2022-09-14 Revised:2022-11-14 Published:2022-11-21
Contact: Jian Hao, Qilong Shen
Supported by:
National Key Research and Development Program of China(2021YFF0701700)

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摘要/Abstract

发展了一个温和条件下可见光促进的含色氨酸的寡肽与YlideFluor试剂的三氟甲基化反应. 初步的机理研究表明在反应过程中1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)与YlideFluor试剂之间形成了一个供体-给体复合物, 在光照条件下, 该复合物被激发后分子中的硫-碳键发生均裂生成三氟甲基自由基, 该自由基进攻寡肽的色氨酸吲哚片段的2-位, 生成相应的三氟甲基修饰的寡肽.

关键词: 氟, 三氟甲基, 色氨酸, 寡肽, 可见光

A photosensitizer-free visible-light-promoted method for site-selective trifluoromethylation of tryptophan- containing oligopeptides using YlideFluor as the trifluoromethyl radical source under mild conditions was developed. Mechanistic studies showed that a donor-acceptor between 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and YlideFluor is generated. Upon irradiation with blue LEDs, the S—CF₃ bond in the adduct undergoes homolytic cleavage to give trifluoromethyl radical, which attacks the electron-rich C-2 position of the indole moiety in the tryptophan-containing oligopeptide.

Key words: fluorine, trifluoromethyl, tryptophan, oligapeptide, visible light

引用此文

刘静, 郝健, 沈其龙. 可见光促进的含色氨酸寡肽与YlideFluor试剂的直接三氟甲基化反应研究[J]. 有机化学, 2023, 43(4): 1517-1524.

Jing Liu, Jian Hao, Qilong Shen. Visible-Light-Promoted Direct Trifluoromethylation of Tryptophan-Containing Oligapeptides with YlideFluor[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1517-1524.

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图/表 5

Figure 1. State-of-the-art of site selective trifluoromethylation of Trp-containing oligopeptides

Entry	Solvent	Base	Light	Time/h	Yield/%
1	DMSO	DBU	Blue	12	60
2	DMSO	DMAP	Blue	12	27
3	DMSO	DIPEA	Blue	12	25
4	DMSO	Cs₂CO₃	Blue	12	18
5	DMSO	NaHCO₃	Blue	12	41
6	CH₃CN	DBU	Blue	12	29
7	DMF	DBU	Blue	12	28
8	DMAc	DBU	Blue	12	22
9	NMP	DBU	Blue	12	18
10	Acetone	DBU	Blue	12	46
11	H₂O	DBU	Blue	12	33
12	THF	DBU	blue	12	2
13	CH₂Cl₂	DBU	Blue	12	45
14	DMSO	DBU	White	12	54
15	DMSO	DBU	Purple	12	56
16	DMSO	DBU		12	46
17	DMSO	DBU	Blue	6	54
18	DMSO	DBU	Blue	9	58
19	DMSO		Blue	12	34
20^c	DMSO			12

Table 1. Optimization of the conditions for reaction of Cbz- Trp-OMe 1a with YlideFluor under irradiation of visible lighta,b

Table 2. Scope of visible-light-promoted trifluoromethylation of Trp-containing oligopeptides with YlideFluora

Entry	Additive	Ylidefluor/equiv.	Yield^a/%
1	TEMPO	1.22	2
2	Under air	0.32	18
3	BHT		42
4	1,4-Dinitrobenzene		50

Table 3. Reaction of Cbz-Trp-OMe 1a with YlideFluor (1.5 equiv.) under irradiation of blue LEDs in the presence of 2.0 equivalents of additive or under air

Figure 2. (Left) UV-Vis-absorption spectroscopic study of a DMSO solution of YlideFluor, DBU and YlideFluor＋DBU; (right) Proposed mechanism for site-selective trifluoromethylation of Trp-containing oligopeptides with YlideFluor

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可见光促进的含色氨酸寡肽与YlideFluor试剂的直接三氟甲基化反应研究

Visible-Light-Promoted Direct Trifluoromethylation of Tryptophan-Containing Oligapeptides with YlideFluor

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