(R)-(+)-1-bromo-3-(1-methylethyl)cyclopentene | 120264-20-2

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: (R)-(+)-1-bromo-3-(1-methylethyl)cyclopentene
• 英文别名: (3S)-1-bromo-3-propan-2-ylcyclopentene
• CAS: 120264-20-2
• 化学式: C₈H₁₃Br
• 分子量: 189.095
• InChiKey: NMOHMVWIXVKUAU-SSDOTTSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (R)-(+)-1-bromo-3-(1-methylethyl)cyclopentene 在 吡啶 、 4-二甲氨基吡啶 、 aluminum oxide 、 氢氧化钾 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 锂硼氢 、 正丁基锂 、 硼烷四氢呋喃络合物 、 双氧水 、 叔丁基锂 、 三异丁基铝 、 二异丁基氢化铝 、 二异丙胺 、 N,N-二异丙基乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 吡啶 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 33.03h， 生成 Selenocarbonic acid O-((1R,3aS,4S,5R,6aR,7S,9aS,10R,10aS)-7-isopropyl-5-methoxymethoxy-1,4,9a-trimethyl-tetradecahydro-dicyclopenta[a,d]cycloocten-10-yl) ester Se-phenyl ester
  参考文献：
  名称：

  (+)-Epoxydictymene的全合成。烷氧基定向环化在二萜结构中的应用

  摘要：

  报道了 (+)-epoxydictymene (1) 的对映选择性合成。对映体纯醛酯 5 与 (S)-3-异丙基环戊烯基锂的缩合选择性地进行以提供 13。一旦该内酯被 Tebbe 试剂亚甲基化，新形成的烯丙基乙烯基醚在三异丁基铝的催化下被诱导进入克莱森重排。所得二环五环辛烯酮衍生物的连续硼氢化-氧化之后是羰基官能团的角甲基化和脱氧。在 C-11 处差向异构化后，α-羟基被区域和立体选择性地引入。一些官能团操纵导致了 57 和 58，当在含有碘代苯二乙酸酯和碘的环己烷溶液中用可见光照射时，两者都经历了有效的环化以提供目标分子的完整骨架。这个关键反应的普遍性，它有效地构建了 1 的应变氧杂双环 [3.3.0] 辛烷亚基，是...

  DOI：

  10.1021/ja971526v
• 作为产物：
  描述：

  3-isopropyl-cyclohexanone 在 吡啶 、 4-二甲氨基吡啶 、 氢氧化钾 、 磺酰氯 、 草酰氯 、 偶氮二异丁腈 、 三氯溴甲烷 、 sodium hydride 、 sodium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 25.0h， 生成 (R)-(+)-1-bromo-3-(1-methylethyl)cyclopentene
  参考文献：
  名称：

  Regioselective conversion of cycloalkanones to vinyl bromides with 1,2-functionality transposition. A general stratagem

  摘要：

  Cyclic beta-keto esters, available by regioselective acylation of cycloalkanone enolates, are rapidly transformed to alpha,beta-unsaturated acids. This functionality transposition allows the derived 3-hydroxy-4-methylthiazole-2-(3H)-thione derivatives to serve as precursors to synthetically useful vinyl bromides. The process involves heating the hydroxamate ester with AIBN in bromotrichloromethane solution. Alkylative and ring contractive variants of the methodology are highlighted. The short sequence makes available precursors to vinyl anions that are not otherwise conveniently accessible.

  DOI：

  10.1021/jo00021a044

文献信息

• Sequenced reactions involving squarate esters. The first suggestion that helical equilibration within the advanced octatetraene intermediate is responsible for stereochemical control
  作者：Leo A. Paquette、Julien Doyon、Kuo Lung Huang

  DOI：10.1016/0040-4039(96)00580-1

  日期：1996.5

  When a chiral (racemic or nonracemic) alkenyl anion is added to a squarate ester, an approximate 1:1 mixture of diastereomers results. Further reaction with a second alkenyl anion leads only to a single product, a finding compatible with helical equilibration at the 1,3,5,7-octatetraene stage of the cascade.

  当将手性（外消旋或非外消旋）烯基阴离子添加到方酸酯中时，会生成约1：1的非对映异构体混合物。与第二个烯基阴离子的进一步反应仅产生单一产物，这一发现与级联的1,3,5,7-辛三烯阶段的螺旋平衡相容。
• Model for diastereomer differentiation during 1,2-addition of chrial (racemic) cyclopentenyl organometallics to [4.2.0] bicyclic enones carrying exocyclic .beta.,.gamma.-double bonds
  作者：Leo A. Paquette、Donald T. DeRussy、Judith C. Gallucci

  DOI：10.1021/jo00271a009

  日期：1989.5
• Exploratory Synthetic Studies Involving the Tricyclo[9.3.0.02,8]tetradecane Ring System Peculiar to the Cyathins
  作者：Karl R. Dahnke、Leo A. Paquette

  DOI：10.1021/jo00083a034

  日期：1994.2

  Following an improved preparation of 2-methylene-1,3-dithiolane, this ketene acetal was shown to undergo inverse-electron-demand Diels-Alder cycloaddition to tropone. Regiocontrolled copper hydride reduction and resolution via sulfoximine adducts was readily achieved to give (-)-9. Addition to 9 of the chiral nonracemic vinyl bromides 21 and 22 proceeded with endo capture of the nucleophilic vinyllithium to give carbinols that underwent anionic oxy-Cope rearrangement at somewhat elevated temperatures. The [3,3] sigmatropic event delivered cis,syn,cis-tricyclo[9.3.0.0(2,8)]tetradecnones possessing structural frameworks related to the cyathins. Once 31 was in hand, it proved an easy matter to introduce added unsaturation and oxygen substituents. The tendency of certain derivatives for transannular cyclization was made quite apparent. Attempts to introduce a C(6)-alpha-methyl substituent was not achieved, chiefly as the result of the overall molecular concavity of this class of intermediates. A variety of reactions aimed at enhancing the level of functionality in rings B and C was explored and processes conducive to the attainment of these goals were developed.
• Total Synthesis of (+)-Epoxydictymene. Application of Alkoxy-Directed Cyclization to Diterpenoid Construction
  作者：Leo A. Paquette、Li-Qiang Sun、Dirk Friedrich、Paul B. Savage

  DOI：10.1021/ja971526v

  日期：1997.9.1

  stereoselectively. Some functional group manipulation led to 57 and 58, both of which underwent efficient cyclization to deliver the complete framework of the target molecule when irradiated with visible light in cyclohexane solution containing iodosobenzene diacetate and iodine. The generality of this key reaction, which efficiently constructs the strained oxabicyclo[3.3.0]octane subunit of 1, is dem...

  报道了 (+)-epoxydictymene (1) 的对映选择性合成。对映体纯醛酯 5 与 (S)-3-异丙基环戊烯基锂的缩合选择性地进行以提供 13。一旦该内酯被 Tebbe 试剂亚甲基化，新形成的烯丙基乙烯基醚在三异丁基铝的催化下被诱导进入克莱森重排。所得二环五环辛烯酮衍生物的连续硼氢化-氧化之后是羰基官能团的角甲基化和脱氧。在 C-11 处差向异构化后，α-羟基被区域和立体选择性地引入。一些官能团操纵导致了 57 和 58，当在含有碘代苯二乙酸酯和碘的环己烷溶液中用可见光照射时，两者都经历了有效的环化以提供目标分子的完整骨架。这个关键反应的普遍性，它有效地构建了 1 的应变氧杂双环 [3.3.0] 辛烷亚基，是...
• Regioselective conversion of cycloalkanones to vinyl bromides with 1,2-functionality transposition. A general stratagem
  作者：Leo A. Paquette、Karl Dahnke、Julien Doyon、Wei He、Kenetha Wyant、Dirk Friedrich

  DOI：10.1021/jo00021a044

  日期：1991.10

  Cyclic beta-keto esters, available by regioselective acylation of cycloalkanone enolates, are rapidly transformed to alpha,beta-unsaturated acids. This functionality transposition allows the derived 3-hydroxy-4-methylthiazole-2-(3H)-thione derivatives to serve as precursors to synthetically useful vinyl bromides. The process involves heating the hydroxamate ester with AIBN in bromotrichloromethane solution. Alkylative and ring contractive variants of the methodology are highlighted. The short sequence makes available precursors to vinyl anions that are not otherwise conveniently accessible.