廉价钴催化下β-D-葡萄烯糖硫苷的立体选择性合成

doi:10.6023/cjoc202202021

摘要/Abstract

报道了以葡萄烯糖-3-吡啶酸酯和硫酚/硫醇为原料, Co(BF₄)₂催化下立体选择性合成β-D-葡萄烯糖硫苷的方法. 目标化合物的化学结构经过了核磁共振、高分辨质谱和单晶X射线衍射的确证. 该反应对各类硫醇和硫酚具有良好的官能团兼容性, 能耐受含酯基、酚/醇羟基、氨基和乙酰氨基等活性硫亲核试剂, 还可用于硫糖肽的高效合成, 为硫糖苷的快速制备提供了新方案.

关键词: Co催化, 糖基化反应, 硫糖苷, 糖肽, 合成

A method of stereoselective synthesis of β-D-thioglycosides from glucosyl-3-pyridinate donor and thiophenols/ thiols catalyzed by Co(BF₄)₂ was reported. The chemical structures of the target compounds were confirmed by nuclear magnetic resonance, high-resolution mass spectrometry and single crystal X-ray diffraction. The reaction has good functional group compatibility with all kinds of mercaptans and thiophenols, and can tolerate active sulfur nucleophiles including ester group, phenol/alcohol hydroxyl group, amino group and acetylamino group. It can also be used for the efficient synthesis of thioglycopeptides, which provides a new way for the rapid preparation of thioglycosides.

Key words: Co-catalysis, glycosylation reaction, thioglycoside, glycopeptide, synthesis

引用此文

华敏, 孙阳星, 张雪晴, 姚辉, 黄年玉. 廉价钴催化下β-D-葡萄烯糖硫苷的立体选择性合成[J]. 有机化学, 2022, 42(7): 2140-2154.

Min Hua, Yangxing Sun, Xueqing Zhang, Hui Yao, Nianyu Huang. Convenient Cobalt-Catalyzed Stereoselective Synthesis of β-D-Thioglucosides[J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2140-2154.

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参考文献 14

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Entry^a	Donor	T/℃	Yield^b/%	β∶α^c
1	1a	120^d	—	—
2	1b	80	55	8∶1
3	1c	80	50	6∶1
4	1d	80	40	3∶1
5	1e	80	57	7∶1
6	1f	80	40	4∶1

Entry^a	Donor	T/℃	Yield^b/%	β∶α^c
1	1a	120^d	—	—
2	1b	80	55	8∶1
3	1c	80	50	6∶1
4	1d	80	40	3∶1
5	1e	80	57	7∶1
6	1f	80	40	4∶1

Entry^a	[Co]	L	Solvent	T/℃	Yield^b/%	β∶α^c
1	Co(acac)₃	CataCXium A	CH₃CN	60	25	7∶1
2	Co(acac)₃	CataCXium A	CH₃CN	100	59	5∶1
3	CoBr₂	CataCXium A	CH₃CN	80	20	1∶3
4	CoCl₂	CataCXium A	CH₃CN	80	32	1∶2
5	Co(PPh₃)₂Cl₂	CataCXium A	CH₃CN	80	35	4∶1
6	Co(acac)₂	CataCXium A	CH₃CN	80	50	6∶1
7	Co(BF₄)₂	CataCXium A	CH₃CN	80	65	8∶1
8	Co(BF₄)₂	Xantphos	CH₃CN	80	45	1∶1
9	Co(BF₄)₂	DPPE	CH₃CN	80	66	6∶1
10	Co(BF₄)₂	(R)-(–)-DTBM-SEGPHOS	CH₃CN	80	53	7∶1
Entry^a	[Co]	L	Solvent	T/℃	Yield^b/%	β∶α^c
11	Co(BF₄)₂	Ph₃P	CH₃CN	80	40	4∶1
12	Co(BF₄)₂	(S,S)-Chiraphos	CH₃CN	80	60	8∶1
13	Co(BF₄)₂	DPPF	CH₃CN	80	71%	7:1
14	Co(BF₄)₂	(R)-(+)-BINAP	CH₃CN	80	80%	10:1
15	Co(BF₄)₂	(S)-(–)-BINAP	CH₃CN	80	50%	2:1
16	Co(BF₄)₂	(R)-(+)-BINAP	DMF	80	-	-
17	Co(BF₄)₂	(R)-(+)-BINAP	THF	80	47%	5:1

Entry^a	[Co]	L	Solvent	T/℃	Yield^b/%	β∶α^c
1	Co(acac)₃	CataCXium A	CH₃CN	60	25	7∶1
2	Co(acac)₃	CataCXium A	CH₃CN	100	59	5∶1
3	CoBr₂	CataCXium A	CH₃CN	80	20	1∶3
4	CoCl₂	CataCXium A	CH₃CN	80	32	1∶2
5	Co(PPh₃)₂Cl₂	CataCXium A	CH₃CN	80	35	4∶1
6	Co(acac)₂	CataCXium A	CH₃CN	80	50	6∶1
7	Co(BF₄)₂	CataCXium A	CH₃CN	80	65	8∶1
8	Co(BF₄)₂	Xantphos	CH₃CN	80	45	1∶1
9	Co(BF₄)₂	DPPE	CH₃CN	80	66	6∶1
10	Co(BF₄)₂	(R)-(–)-DTBM-SEGPHOS	CH₃CN	80	53	7∶1
Entry^a	[Co]	L	Solvent	T/℃	Yield^b/%	β∶α^c
11	Co(BF₄)₂	Ph₃P	CH₃CN	80	40	4∶1
12	Co(BF₄)₂	(S,S)-Chiraphos	CH₃CN	80	60	8∶1
13	Co(BF₄)₂	DPPF	CH₃CN	80	71%	7:1
14	Co(BF₄)₂	(R)-(+)-BINAP	CH₃CN	80	80%	10:1
15	Co(BF₄)₂	(S)-(–)-BINAP	CH₃CN	80	50%	2:1
16	Co(BF₄)₂	(R)-(+)-BINAP	DMF	80	-	-
17	Co(BF₄)₂	(R)-(+)-BINAP	THF	80	47%	5:1

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