| 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 | |
| Alternative Title | 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 Zunhua1; Kim Kyung Ran2; Park AhYoung2; Lee HyungRock2; Kang JinAh2; Kim Won Hee2; Chun Pusoon2; Gong Ping1; Lee Boeun4; Jeong Lak Shin5; Moon Hyung Ryong2 | |
| 2009 | |
| Source Publication | CHINESE JOURNAL OF CHEMISTRY
 |
| ISSN | 1001-604X |
| Volume | 27Issue:12Pages:2405-2412 |
| Abstract | 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. |
| Other Abstract | 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. |
| Keyword | 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 |
| Indexed By | CSCD |
| Language | 英语 |
| Funding Project | [Korean Government (MOEHRD)] |
| CSCD ID | CSCD:3788684 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.imr.ac.cn/handle/321006/143833 |
| Collection | 中国科学院金属研究所 |
| Affiliation | 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 |
| Recommended Citation 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. |
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