三氟甲磺酸钪催化嘌呤与邻羟基苄醇反应构建非环核苷

doi:10.6023/cjoc202106010

有机化学 ›› 2021, Vol. 41 ›› Issue (11): 4391-4399.DOI: 10.6023/cjoc202106010 上一篇下一篇

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研究论文

三氟甲磺酸钪催化嘌呤与邻羟基苄醇反应构建非环核苷

夏超^a, 王东超^b, 郭海明^a^,^b^,^*()

a 河南师范大学环境学院河南新乡 453007
b 河南师范大学化学化工学院绿色化学介质与反应教育部重点实验室精细化学品绿色制造河南省协同创新中心河南省有机功能分子与药物创新重点实验室河南新乡 453007

收稿日期:2021-06-05 修回日期:2021-07-16 发布日期:2021-08-17
通讯作者: 郭海明
基金资助:
国家自然科学基金(22071046); 中原学者(212101510004); 中央引导地方科技发展专项资金(YDZX20204100001786)

Sc(OTf)₃-Catalyzed Reaction of Purines with o-Hydroxybenzyl Alcohols for Construction of Acyclic Nucleosides

Chao Xia^a, Dongchao Wang^b, Haiming Guo^a^,^b()

a School of Environment, Henan Normal University, Xinxiang, Henan 453007
b Henan Key Laboratory of Organic Functional Molecules and Drug Innovation, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007

Received:2021-06-05 Revised:2021-07-16 Published:2021-08-17
Contact: Haiming Guo
Supported by:
National Natural Science Foundation of China(22071046); Zhongyuan Scholar(212101510004); National Government Guides Local Special Funds for the Development of Science and Technology(YDZX20204100001786)

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摘要/Abstract

通过三氟甲磺酸钪催化, 在温和条件下实现了邻羟基苄醇与嘌呤的烷基化反应. 该C—N键形成的过程可能是通过邻亚甲基苯醌中间体进行的. 以优秀的产率(最高可达96%)高效地合成了一系列非环核苷类似物, 底物范围广. 反应规模放大后, 产率保持不变.

关键词: 嘌呤非环核苷, 邻亚甲基苯醌, 钪催化, 烷基化反应

Efficient alkylation of purines with ortho-hydroxybenzyl alcohols under mild condition has been achieved by Sc(OTf)₃ catalysis. This C—N bond formation process is proposed to proceed through an ortho-quinone methide intermediate. The reaction allows for efficient synthesis of various acyclic nucleoside analogs, with excellent yields of up to 96%, across a broad range of substrates and the yields were maintained as the reactions were scaled up.

Key words: purine acyclic nucleosides, ortho-quinone methide, scandium catalysis, alkylation reaction

引用此文

夏超, 王东超, 郭海明. 三氟甲磺酸钪催化嘌呤与邻羟基苄醇反应构建非环核苷[J]. 有机化学, 2021, 41(11): 4391-4399.

Chao Xia, Dongchao Wang, Haiming Guo. Sc(OTf)₃-Catalyzed Reaction of Purines with o-Hydroxybenzyl Alcohols for Construction of Acyclic Nucleosides[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4391-4399.

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图/表 7

图式1. (a)邻亚甲基苯醌的共轭加成反应、(b)邻亚甲基苯醌参与的C—N键生成反应和(c)本文的工作

Scheme 1. (a) Conjugate addition reaction of o-QMs, (b) C—N bond formation with o-QMs, and (c) this work

Entry	LA (x)	Solvent	t/h	Yield^b/%
1	In(OTf)₃ (20)	DCM	12	75
2	Cu(OTf)₂ (20)	DCM	12	68
3	Fe(OTf)₃ (20)	DCM	12	71
4	Sc(OTf)₃ (20)	DCM	12	95
5	Y(OTf)₃ (20)	DCM	12	18
6	Mg(OTf)₂ (20)	DCM	12	10
7	Zn(OTf)₂ (20)	DCM	12	NR
8	TfOH (10)	DCM	12	20
9	Sc(OTf)₃ (10)	DCM	5	94
10	Sc(OTf)₃ (5)	DCM	10	94
11	Sc(OTf)₃ (2.5)	DCM	24	68
12^c	Sc(OTf)₃ (2.5)	DCM	24	58
13^d	Sc(OTf)₃ (2.5)	DCM	24	61
14^e	Sc(OTf)₃ (2.5)	DCM	24	55
15	Sc(OTf)₃ (5)	Toluene	10	74
16	Sc(OTf)₃ (5)	Et₂O	10	NR
17	Sc(OTf)₃ (5)	Acetone	10	81
18	Sc(OTf)₃ (5)	THF	10	NR
19	Sc(OTf)₃ (5)	EA	10	78

表1. 反应条件的优化a

Table 1. Optimization of the reaction conditions

表2. 嘌呤类化合物底物范围a

Table 2. Substrate scope of purine compounds

表3. 邻羟基苄醇类化合物底物范围a

Table 3. Substrate scope of ortho-hydroxybenzyl alcohol compounds

图式2. 克级规模合成

Scheme 2. Gram-scale synthesis

图式3. 4-羟基喹唑啉与邻羟基苄醇的反应

Scheme 3. Reaction of 4-hydroxyquinazoline with o-hydroxy- benzyl alcohol

Entry	Yield^b/%	ee^c/%
1	33	20
2	NR	—
3	41	55

表4. 不对称催化的初步尝试a

Table 4. Preliminary investigation on the catalytic asymmetric version

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三氟甲磺酸钪催化嘌呤与邻羟基苄醇反应构建非环核苷

Sc(OTf)₃-Catalyzed Reaction of Purines with o-Hydroxybenzyl Alcohols for Construction of Acyclic Nucleosides

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三氟甲磺酸钪催化嘌呤与邻羟基苄醇反应构建非环核苷

Sc(OTf)3-Catalyzed Reaction of Purines with o-Hydroxybenzyl Alcohols for Construction of Acyclic Nucleosides

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Sc(OTf)₃-Catalyzed Reaction of Purines with o-Hydroxybenzyl Alcohols for Construction of Acyclic Nucleosides