PhSO3CH2F: 一种用于乙酰丙酮衍生物O-一氟甲基化的新型试剂

doi:10.6023/cjoc202203004

有机化学 ›› 2022, Vol. 42 ›› Issue (11): 3798-3804.DOI: 10.6023/cjoc202203004 上一篇下一篇

所属专题：有机氟化学虚拟合辑

研究论文

PhSO₃CH₂F: 一种用于乙酰丙酮衍生物O-一氟甲基化的新型试剂

李珊^a^,^b, 蒋绿齐^a^,^*()

^a南京理工大学化工学院南京 210094
^b沙洲职业工学院江苏张家港 215600

收稿日期:2022-03-01 修回日期:2022-06-01 发布日期:2022-07-13
通讯作者: 蒋绿齐
基金资助:
国家自然科学基金(21776138); 国家自然科学基金(22078161); 国家自然科学基金(22108124); 中央高校基本科研业务费专项资金(30918011314); 江苏省自然科学基金(BK20141394); 江苏省青蓝工程((2022)29); 江苏省青蓝工程

PhSO₃CH₂F: A New Reagent for O-Monofluoromethylation of Acetylacetone Derivatives

Shan Li^a^,^b, Lüqi Jiang^a()

^aChemical Engineering College, Nanjing University of Science and Technology, Nanjing 210094
^bShazhou Professional Institute of Technology, Zhangjiagang, Jiangsu 215600

Received:2022-03-01 Revised:2022-06-01 Published:2022-07-13
Contact: Lüqi Jiang
Supported by:
National Natural Science Foundation of China(21776138); National Natural Science Foundation of China(22078161); National Natural Science Foundation of China(22108124); Fundamental Research Funds for the Central Universities(30918011314); Natural Science Foundation of Jiangsu Province(BK20141394); Six Talent Peaks Project in Jiangsu Province

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摘要/Abstract

开发了一种性状稳定且易于放大合成规模的一氟甲基化试剂——一氟代苯磺酸甲酯(PhSO₃CH₂F). 该试剂能够与乙酰丙酮衍生物反应, 在温和条件下以高选择性和良好的收率得到相应的O-一氟甲基化产物, 此外, 该试剂还可以对复杂分子进行后修饰. 这种新方法为一氟甲基化合物的合成提供了更多选择.

关键词: 一氟代苯磺酸甲酯, 乙酰丙酮衍生物, 一氟甲基化

A new shelf-stable and easily scalable monofluoromethylating reagent, fluoromethyl benzenesulfonate (PhSO₃CH₂F), was developed. This reagent is able to react with acetylacetone derivatives to afford corresponding O-monofluoromethylated products in high selectivity and good yields under mild conditions. Moreover, the method could be used in late-stage monofluoromethylation. This method provides more options for the synthesis of monofluoromethyl compounds.

Key words: fluoromethyl benzenesulfonate, acetylacetone derivatives, monofluoromethylation

引用此文

李珊, 蒋绿齐. PhSO₃CH₂F: 一种用于乙酰丙酮衍生物O-一氟甲基化的新型试剂[J]. 有机化学, 2022, 42(11): 3798-3804.

Shan Li, Lüqi Jiang. PhSO₃CH₂F: A New Reagent for O-Monofluoromethylation of Acetylacetone Derivatives[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3798-3804.

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图/表 6

图1. 直接一氟甲基化试剂

Figure 1. Direct monofluoromethylating reagents

图式1. 试剂2的合成

Scheme 1. Synthesis of reagent 2

Entry	Base	Solvent	Temp./℃	Yield^b/%
1	K₂CO₃	MeCN	r.t.	24
2	NaHCO₃	MeCN	r.t.	Trace
3	Cs₂CO₃	MeCN	r.t.	36
4	C_SF	MeCN	r.t.	67
5	CsOH•H₂O	MeCN	r.t.	27
6	KF	MeCN	r.t.	59
7	DBU	MeCN	r.t.	NR
8	DIPEA	MeCN	r.t.	NR
9	Et₃N	MeCN	r.t.	NR
10	C_SF	DMF	r.t.	82
11	C_SF	PhMe	r.t.	43
12	C_SF	CH₂Cl₂	r.t.	62
13	C_SF	NMP	r.t.	50
14	C_SF	DMF	0	37
15	C_SF	DMF	50	84
16^c	C_SF	DMF	r.t.	75
17^d	C_SF	DMF	r.t.	80

表1. 反应条件筛选a

Table 1. Optimization of the reaction conditions

表2. 试剂2 和乙酰丙酮衍生物的一氟甲基化反应底物拓展a

Table 2. Scope of monofluoromethylation of acetylacetone derivatives with reagent 2

图式2. 可能的反应机理

Scheme 2. Proposed mechanism

图1. 反应1 h后氟谱跟踪结果

Figure 1. 19F NMR tracking results after 1 h reaction

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PhSO₃CH₂F: 一种用于乙酰丙酮衍生物O-一氟甲基化的新型试剂

PhSO₃CH₂F: A New Reagent for O-Monofluoromethylation of Acetylacetone Derivatives

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