ethyl (+/-)-(1R,2R,3R,4S)-3-bromobicyclo[2.2.1]hept-5-ene-2-carboxylate | 99187-47-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl (+/-)-(1R,2R,3R,4S)-3-bromobicyclo[2.2.1]hept-5-ene-2-carboxylate
• 英文别名: (+/-)-3endo-bromo-norborn-5-ene-2endo-carboxylic acid ethyl ester；(+/-)-3endo-Brom-norborn-5-en-2endo-carbonsaeure-aethylester；ethyl (1R,2R,3R,4S)-3-bromobicyclo[2.2.1]hept-5-ene-2-carboxylate
• CAS: 99187-47-0
• 化学式: C₁₀H₁₃BrO₂
• 分子量: 245.116
• InChiKey: CDPQUBQJMSRTPW-UYXSQOIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl (+/-)-(1R,2R,3R,4S)-3-bromobicyclo[2.2.1]hept-5-ene-2-carboxylate 在 盐酸 、 sodium periodate 、 四氧化锇 、 锂硼氢 、 N-甲基吲哚酮 、 溴 、 sodium 、 dinitrogen tetraoxide 、 碳酸氢钠 、 臭氧 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 silver(l) oxide 、 肼 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 氨 、 水 、 丙酮 、 苯 为溶剂， 反应 192.0h， 生成 (1R,2S,3R,5R)-3-氨基-5-(羟甲基)环戊烷-1,2-二醇
  参考文献：
  名称：

  Carbocyclic Nucleoside Analogs. 1. Concise Enantioselective Synthesis of Functionalized Cyclopentanes and Formal Total Synthesis of Aristeromycin

  摘要：

  An enantioselective synthesis of functionalized cyclopentanes has been used to access carbocyclic nucleoside analogs. This pathway allows access to carbocyclic C- or carbocyclic N-nucleosides from a common intermediate, ester 16. Additionally, (1R,2R,3S,4R)-4-amino-2,3-dihydroxy-1-cyclopentanemethanol (18), an intermediate in the total synthesis of aristeromycin, has been prepared as a single enantiomer in eight isolated steps from cyclopentadiene. Progress toward the synthesis of novel carbocyclic C-nucleosides is also discussed.

  DOI：

  10.1021/jo970153d
• 作为产物：
  描述：

  (+/-)-3endo-bromo-norborn-5-ene-2endo-carboxylic acid 生成 ethyl (+/-)-(1R,2R,3R,4S)-3-bromobicyclo[2.2.1]hept-5-ene-2-carboxylate
  参考文献：
  名称：

  Genetic and Biogeographic Relationships of the Invasive Round (Neogobius melanostomus) and Tubenose (Proterorhinus marmoratus) Gobies in the Great Lakes Versus Eurasian Populations

  摘要：

  Population genetic structure and systematic relationships were investigated for two exotic fishes introduced to the Great Lakes in 1990, the round goby Neogobius melanostomus and the tubenose goby Proterorhinus marmoratus, using DNA sequences from the left domain of the mitochondrial DNA control region. Samples of round gobies were compared from different sites in the Great Lakes, an introduced population from the Gulf of Gdansk in Poland, and a native population from the northern Black Sea. The round goby was characterized by, relatively high genetic variability, and 17 haplotypes were identified from 64 individuals. Levels of genetic variation for the round goby were similar in the invasive and native sampling sites, suggesting relatively large founding populations and lack of bottlenecks. The northern Black Sea was eliminated as a probable founding source for both the Great Lakes and the exotic population in Poland. Substitutions in the left domain of the control region revealed significant differences among samples from the Great Lakes and Eurasia, and between Lakes Erie and St. Clair, suggesting non-random mating. No variation was detected in the tubenose goby population in the Great Lakes, which has been less successful in terms of spread and population growth. A molecular clock calibration suggested that the genera Neogobius and Proterorhinus diverged about 5.2 +/- 1.0 million years ago, apparently separating from a common ancestor shared with Gobius during the isolation of the Paratethys basin from the Mediterranean Tethys Sea.

  DOI：

  10.1016/s0380-1330(01)70642-9

文献信息

• Synthesis of Novel Carbocyclic Nucleoside Analogues Containing Bicyclo[2.2.1]hept-2-ene-2-methanol
  作者：Hubert Hřebabecký、Martin Dračínský、Antonín Holý

  DOI：10.1135/cccc20080044

  日期：——

  Starting ethyl (1R*,2R*,3R*,4S*)-3-bromobicyclo[2.2.1]hept-5-ene-2-carboxylate (9) was reduced with LiAlH₄and benzoylated giving [(1R*,2R*,3R*,4S*)-3-bromobicyclo[2.2.1]hept-5-en-2-yl]methyl benzoate (11). Treatment of11with NaN₃and CrO₃in acetic acid afforded [(1R*,2S*,3R*,4R*,5S*,6R*)-6-azido-3-bromo-5-hydroxybicyclo[2.2.1]hept-2-yl]methyl benzoate (12a) and [(1R*,2S*,3S*,4R*,5S*,6R*)-5-azido-3-bromo-6-hydroxybicyclo[2.2.1]heptan-2-yl]-methyl benzoate (12b). These key intermediates were separated and converted in five reaction steps to (1R*,2R*,3S*,4S*)-3-[(5-amino-6-chloropyrimidin-4-yl)amino]-5-(hydroxymethyl)- bicyclo[2.2.1]hept-5-en-2-ol (17a) and (1R*,2R*,3S*,4S*)-3-[(5-amino-6-chloropyrimidin-4-yl)- amino]-6-(hydroxymethyl)bicyclo[2.2.1]hept-5-en-2-ol (17b). Ring closure with triethyl orthoformate led to (1R*,2R*,3S*,4S*)-5-(chloromethyl)-3-(6-chloro-9H-purin-9-yl)bicyclo[2.2.1]hept-5-en-2-ol (18a) and (1R*,2R*,3S*,4S*)-6-(chloromethyl)-3-(6-chloro-9H-purin-9-yl)- bicyclo[2.2.1]hept-5-en-2-ol (18b) using hydrochloric acid as a catalyst or (1R*,2R*,3S*,4S*)-3-(6-chloro-9H-purin-9-yl)-5-(hydroxymethyl)bicyclo[2.2.1]hept-5-en-2-ol (19a) and (1R*,2R*,3S*,4S*)- 3-(6-chloro-9H-purin-9-yl)-6-(hydroxymethyl)bicyclo[2.2.1]hept-5-en-2-ol (19b) using trifluoro- acetic acid as a catalyst. From19aand19b, 6-amino- and 6-(cyclopropylamino)purine derivatives20and21were prepared.

  使用LiAlH₄和苯甲酰化剂对起始物乙基(1R*,2R*,3R*,4S*)-3-溴代双环[2.2.1]庚-5-烯-2-羧酸酯(9)进行还原和苯甲酰化，得到[(1R*,2R*,3R*,4S*)-3-溴代双环[2.2.1]庚-5-烯-2-基]甲基苯甲酸酯(11)。将11与NaN₃和CrO₃在乙酸中处理，得到[(1R*,2S*,3R*,4R*,5S*,6R*)-6-叠氮-3-溴代-5-羟基双环[2.2.1]庚-2-基]甲基苯甲酸酯(12a)和[(1R*,2S*,3S*,4R*,5S*,6R*)-5-叠氮-3-溴代-6-羟基双环[2.2.1]庚烷-2-基]-甲基苯甲酸酯(12b)。这些关键中间体被分离并在五个反应步骤中转化为(1R*,2R*,3S*,4S*)-3-[(5-氨基-6-氯嘧啶-4-基)氨基]-5-(羟甲基)-双环[2.2.1]庚-5-烯-2-醇(17a)和(1R*,2R*,3S*,4S*)-3-[(5-氨基-6-氯嘧啶-4-基)氨基]-6-(羟甲基)-双环[2.2.1]庚-5-烯-2-醇(17b)。使用三乙基正酯酸酯进行环合反应，用盐酸作为催化剂得到(1R*,2R*,3S*,4S*)-5-(氯甲基)-3-(6-氯-9H-嘌呤-9-基)双环[2.2.1]庚-5-烯-2-醇(18a)和(1R*,2R*,3S*,4S*)-6-(氯甲基)-3-(6-氯-9H-嘌呤-9-基)-双环[2.2.1]庚-5-烯-2-醇(18b)，或用三氟乙酸作为催化剂得到(1R*,2R*,3S*,4S*)-3-(6-氯-9H-嘌呤-9-基)-5-(羟甲基)-双环[2.2.1]庚-5-烯-2-醇(19a)和(1R*,2R*,3S*,4S*)-3-(6-氯-9H-嘌呤-9-基)-6-(羟甲基)-双环[2.2.1]庚-5-烯-2-醇(19b)。从19a和19b中制备6-氨基和6-(环丙基氨基)嘌呤衍生物20和21。