(+)-2-n-Propylapopinene | 129444-04-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+)-2-n-Propylapopinene
• 英文别名: (1S,5R)-6,6-dimethyl-2-propylbicyclo[3.1.1]hept-2-ene
• CAS: 129444-04-8
• 化学式: C₁₂H₂₀
• 分子量: 164.291
• InChiKey: ZMJCSPWTNHCBKZ-GHMZBOCLSA-N

物化性质

• 沸点：
  202.6±7.0 °C(Predicted)
• 密度：
  0.869±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  (+)-2-n-Propylapopinene 、 alkaline earth salt of/the/ methylsulfuric acid 以 四氢呋喃 为溶剂， 反应 24.0h， 以93%的产率得到9-[(1R,2S,3R,5R)-6,6-dimethyl-2-propyl-3-bicyclo[3.1.1]heptanyl]-9-borabicyclo[3.3.1]nonane
  参考文献：
  名称：

  Hydroboration. 94. Rates of Hydroboration of 2-Organylapopinenes with 9-Borabicyclo[3.3.1]nonane, Providing B-(2-Organylapoisopinocampheyl)-9-borabicyclo[3.3.1]nonanes, Potentially Valuable for the Asymmetric Reduction of Prochiral Ketones

  摘要：

  Five representative enantiomerically pure, hindered terpenes, derived from a-pinene, namely 8-organylapopinenes (2-R-apopinenes, R = Et, Pr, i-Bu, Ph, and i-Pr) have been treated with 9-borabicyclo[3.3.1]nonane (9-BBN) in a 1:1 molar ratio in THF at 24 degrees C and the rate of hydroboration followed. Increasing the bulk of the 2-R group from the 2-methyl of alpha-pinene (Ipc, 2-methylapopinene) to 8-ethyl-(Eap), to 2-propyl-(Prap), to 2-isobutyl-(i-Bap), to 2-phenyl-(Pap), and to 2-isopropyl-(i-Prap) significantly lowers the rate of hydroboration with 9-BBN. Thus, the rate of hydroboration of alpha-pinene with 9-BBN is faster than the rates for the 2-R-apopinenes studied. The sterically bulkier 2-isobutyl-, 2-phenyl-, and 2-isopropylapopinenes reveal a significantly slower rate of hydroboration with 9-BBN. At an elevated temperature, 65 degrees C, the reaction of 9-BBN (1.0 equiv) with a slight excess of optically pure 2-isobutyl- and 2-phenylapopinenes (1.10-1.20 equiv), under neat conditions, is facilitated to provide the desired B-(2-organylapoisopinocampheyl)-9-borabicyclo[3.3.1]nonanes (2-organyl = isobutyl- and phenyl) in quantitative yield. Unfortunately, this synthesis failed for 2-isopropylapopinene. Fortunately, an indirect synthesis proved satisfactory. Treatment of enantiomerically pure (2-isopropylapoisopinocampheyl)borane, i-PrapBH(2), conveniently synthesized from 2-isopropylapopinene, and 1,5-cyclooctadiene (1,5-COD), provided, after thermal isomerization, the desired 1:1 adduct [B-(2-Rap)-9-BBN; 2-Rap = 2-isopropylapoisopinyl skeleton] in quantitative yield. Consequently, five of the 2-R-apopinenes, R = Et, Pr, i-Bu, Ph, and i-Pr, have been successfully converted into the corresponding B-(2-Rap)-9-BBN derivatives.

  DOI：

  10.1021/jo9617169
• 作为产物：
  描述：

  桃金娘烯醇 在 乙醚 、 三溴化磷 作用下， 生成 (+)-2-n-Propylapopinene
  参考文献：
  名称：

  Rupe, Justus Liebigs Annalen der Chemie, 1927, vol. 459, p. 179

  摘要：

  DOI：

文献信息

• Activated alkyl- and allyl-alkali metal reagents: Contrasting behaviour towards ethylene
  作者：Constantinos G. Screttas、Barry R. Steele

  DOI：10.1016/0022-328x(93)83106-6

  日期：1993.7

  regioselectivity of the reaction of metallated hex-1-ene and (+)-α-pinene with CO2 could be substantially modified by the addition of Mg(OCH2CH2OEt)2. Addition of the latter also solubilizes the organometallic reagents. The allylmetallic products from the metallation of hex-1-ene and α-pinene added to ethylene under mild conditions. Whereas up to four molecules of ethylene added to metallated hex-1-ene, only one

  乙烯，己烯-1-己烯和（+）-α- pine烯很容易在甲基环己烷中以n BuLi / LiK（OCH 2 CH 2 NMe 2）2系统金属化。通过添加Mg（OCH 2 CH 2 OEt）2可以大大改变金属化的1-己烯和（+）-α-pine烯与CO 2的反应的区域选择性。。后者的添加也溶解了有机金属试剂。在温和条件下，将己烯-1-烯和α-pine烯金属化的烯丙基金属产物添加到乙烯中。尽管最多有四个乙烯分子被添加到金属化的1--1-烯中，但是根据反应物的比例，只有一个或两个被添加到金属化的α-pine烯中。涉及使用多种其他强碱（例如n BuLi / t C 5 H 11 OK和n BuM（M（Li，Na，K），添加和不添加TMEDA）的类似反应表明存在叔胺，除了有助于金属化反应外，对于添加的发生是必不可少的。
• Selective reductions. 46. Effect of the steric requirement at the 2-position of apopinene on chiral reductions. B-(iso-2-ethylapopinocampheyl)- and B-(iso-2-n-propylapopinocampheyl)-9-borabicyclo[3.3.1]nonanes as improved reagents for the chiral reduction of .alpha.,.beta.-acetylenic ketones and .alpha.-keto esters
  作者：Herbert C. Brown、P. Veeraraghavan Ramachandran、Steven A. Weissman、S. Swaminathan

  DOI：10.1021/jo00313a020

  日期：1990.12

  B-(Iso-2-ethylapopinocampheyl)-9-borabicyclo[3.3.1]nonane (Eapine-Borane, 7), and B-(Iso-2-n-propylapopinocampheyl)-9-borabicyclo[3.3.1]nonane (Prapine-Borane, 9), prepared via the hydroboration of 2-ethylapopinene (6) or 2-n-propylapopinene (8), respectively, with 9-borabicyclo[3.3.1]nonane, reduce prochiral alpha,beta-acetylenic ketones and alpha-keto esters to the corresponding alcohols with significantly higher optical induction than does Alpine-Borane (1). (-)-2-n-Propylapopinene was synthesized by treating nopyl tosylate with dimethyl cuprate prepared in situ from ethyllithium and cuprous iodide. (+)-2-n-Propylapopinene was synthesized by Schlosser metalation of (+)-alpha-pinene followed by treatment with ethyl iodide. 4-Phenyl-3-butyn-2-one was reduced to the corresponding propargylic alcohol in 89% ee and 96% ee by Eapine-Borane and Prapine-Borane, respectively, as compared to 82% ee with Alpine-Borane. Similar improved results were realized in the reduction of other acetylenic ketones by Eapine-Borane and Prapine-Borane. Similar improvements in the optical yields were realized in the reduction of alpha-keto esters by Eapine-Borane. For example, while Alpine-Borane produced methyl and ethyl lactate in 92% and 91% ee, respectively, Eapine-Borane gave these alcohols in 97% and 96% ee, respectively. Unfortunately, Prapine-Borane shows no improvement in percent ee for the reduction of alpha-keto esters. The increase in the percent ee realized is tentatively attributed to the increased steric requirements of the alkyl group at the 2-position of apopinene.
• Hydroboration of Terpenes. 11. Convenient Method for Upgrading 2-Organylapopinenes to High Optical Purity by Reaction of 2-Organylapoisopinocampheylboranes with Suitable Dienes Followed by Displacement with Acetaldehyde
  作者：Herbert C. Brown、Ulhas P. Dhokte

  DOI：10.1021/jo00097a065

  日期：1994.9
• BROWN, HERBERT C.;VEERARAGHAVAN, RAMACHANDRAN P.;WEISSMAN, STEVEN A.;SWAM+, J. ORG. CHEM., 55,(1990) N6, C. 6328-6333
  作者：BROWN, HERBERT C.、VEERARAGHAVAN, RAMACHANDRAN P.、WEISSMAN, STEVEN A.、SWAM+

  DOI：——

  日期：——
• Rupe, Justus Liebigs Annalen der Chemie, 1927, vol. 459, p. 179
  作者：Rupe

  DOI：——

  日期：——