Highly Concise Synthesis of 3 '-\Up\-ethynyl-5 '-methylbicyclo3.1.0hexyl Purine and Pyrimidine Nucleoside Derivatives Using Rhodium(II) Carbenoid Cycloaddition and Highly Diastereoselective Grignard Reaction

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	Highly Concise Synthesis of 3 '-\Up\-ethynyl-5 '-methylbicyclo3.1.0hexyl Purine and Pyrimidine Nucleoside Derivatives Using Rhodium(II) Carbenoid Cycloaddition and Highly Diastereoselective Grignard Reaction
其他题名	Highly Concise Synthesis of 3'-"Up"-ethynyl-5'-methylbicyclo-3.1.0-hexyl Purine and Pyrimidine Nucleoside Derivatives Using Rhodium(II) Carbenoid Cycloaddition and Highly Diastereoselective Grignard Reaction
	Yang Zunhua 1; Kim Kyung Ran 2; Park AhYoung 2; Lee HyungRock 2; Kang JinAh 2; Kim Won Hee 2; Chun Pusoon 2; Gong Ping 1; Lee Boeun 4; Jeong Lak Shin 5; Moon Hyung Ryong 2
	2009
发表期刊	CHINESE JOURNAL OF CHEMISTRY
ISSN	1001-604X
卷号	27 期号:12 页码:2405-2412
摘要	Synthesis of north-5'-methylbicyclo3.1.0hexyl purine and pyrimidine nucleosides with an ethynyl group at C-3' position has been successfully accomplished by a facile method. Methylbicyclo3.1.0hexanone (+/-)-5 having three contiguous chiral centers was remarkably simply constructed only by four steps containing a carbenoid insertion reaction in the presence of rhodium(II) acetate dimer and CuSO(4), giving a correct relative stereochemistry of the generated three chiral centers. Upon Grignard reaction of (+/-)-5 with ethynyl magnesium bromide, exclusive diastereoselectivity was observed. Condensation of glycosyl donor (+/-)-9 with purine nucleobase afforded only the desired N(9)-alkylated nucleoside, while condensation with pyrimidine, N(3)-benzoylated uracil gave the desired N(1)-alkylated nucleoside (+/-)-13 with the undesired O(2)-alkylated nucleoside (+/-)-14. Probably, (+/-)-14 would be formed due to steric hindrance caused upon approaching for N(1)-alkylation.
其他摘要	Synthesis of nortA-5'-inethylbicyclo3.1.0hexyl purine and pyrimidine nucleosides with an ethynyl group at C-3' position has been successfully accomplished by a facile method. Methylbicyclo3.1.0hexanone (±)-5 having three contiguous chiral centers was remarkably simply constructed only by four steps containing a carbenoid insertion reaction in the presence of rhodium(Ⅱ) acetate dimer and CuSO4, giving a correct relative stereochemistry of the generated three chiral centers. Upon Grignard reaction of (+ )-5 with ethynylmagnesium bromide, exclusive di-astereoselectivity was observed. Condensation of glycosyl donor (±)-9 with purine nucleobase afforded only the desired N~9-alkylated nucleoside, while condensation with pyrimidine, N~3-benzoylated uracil gave the desired N~1'-alkylated nucleoside (±)-13 with the undesired O~2-alkylated nucleoside (±)-14. Probably, (±)-14 would be formed due to steric hindrance caused upon approaching for N~1-alkylation.
关键词	ADENOSINE RECEPTOR AGONISTS POTENTIAL ANTIVIRAL AGENTS ANTI-HIV AGENT CARBOCYCLIC NUCLEOSIDES STEREOSELECTIVE-SYNTHESIS INTRAMOLECULAR CYCLOPROPANATION ENANTIOSELECTIVE SYNTHESIS CONFORMATIONAL-ANALYSIS BROAD-SPECTRUM NEPLANOCIN-C cycloaddition diastereoselective bicyclo3.1.0hexanone north conformation steric hindrance
收录类别	CSCD
语种	英语
资助项目	[Korean Government (MOEHRD)]
CSCD记录号	CSCD:3788684
引用统计
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/143833
专题	中国科学院金属研究所
作者单位	1.中国科学院金属研究所 2.中国科学院广州生物医药与健康研究院 3.Pusan Natl Univ, Res Institute Drug Dev, Pusan 609735, South Korea 4.Seoul Natl University, Coll Pharm, Seoul 151742, South Korea 5.梨花女子大学
推荐引用方式 GB/T 7714	Yang Zunhua,Kim Kyung Ran,Park AhYoung,et al. Highly Concise Synthesis of 3 '-\Up\-ethynyl-5 '-methylbicyclo3.1.0hexyl Purine and Pyrimidine Nucleoside Derivatives Using Rhodium(II) Carbenoid Cycloaddition and Highly Diastereoselective Grignard Reaction[J]. CHINESE JOURNAL OF CHEMISTRY,2009,27(12):2405-2412.
APA	Yang Zunhua.,Kim Kyung Ran.,Park AhYoung.,Lee HyungRock.,Kang JinAh.,...&Moon Hyung Ryong.(2009).Highly Concise Synthesis of 3 '-\Up\-ethynyl-5 '-methylbicyclo3.1.0hexyl Purine and Pyrimidine Nucleoside Derivatives Using Rhodium(II) Carbenoid Cycloaddition and Highly Diastereoselective Grignard Reaction.CHINESE JOURNAL OF CHEMISTRY,27(12),2405-2412.
MLA	Yang Zunhua,et al."Highly Concise Synthesis of 3 '-\Up\-ethynyl-5 '-methylbicyclo3.1.0hexyl Purine and Pyrimidine Nucleoside Derivatives Using Rhodium(II) Carbenoid Cycloaddition and Highly Diastereoselective Grignard Reaction".CHINESE JOURNAL OF CHEMISTRY 27.12(2009):2405-2412.