(1R)-exo-3-(methylthio)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-one | 114611-89-1

• 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: (1R)-exo-3-(methylthio)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-one
• 英文别名: 3-(exo-Methylthio)camphor；(1R)-exo-3-(methylthio)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one；(1R,3R,4S)-1,7,7-trimethyl-3-methylsulfanylbicyclo[2.2.1]heptan-2-one
• CAS: 114611-89-1
• 化学式: C₁₁H₁₈OS
• 分子量: 198.329
• InChiKey: SQYCDCHRERYZCI-XLDPMVHQSA-N

物化性质

• 沸点：
  135-140 °C(Press: 0.5 Torr)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.74
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1R)-exo-3-(methylthio)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-one 在 二异丁基氢化铝 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以82%的产率得到(+)-exo-3-(Methylthio)-1,7,7-trimethylbicyclo<2.2.1>heptan-2-ol
  参考文献：
  名称：

  通过樟脑衍生的Y叶立德叶酸制备对映体富集的（2R，3R）-或（2S，3S）-反式-2,3-二芳基环氧乙烷。

  摘要：

  容易获得的D-（+）-樟脑胶衍生的硫化物3、4、6和7通过叶立德途径用于对映选择性环氧化。当使用苄基化或甲基化硫化物作为亚苄基转移的试剂或介体时，分别实现了化学计量和催化环氧化。仅当使用包含exo-（3和4）和end-（6和7）烷硫基的硫化物时，才能实现相反的不对称诱导。即，在相同的手性池衍生试剂中，在极其温和的条件下，可以以极高的收率和中等至良好的ee值获得（+）-和（-）-反式-二芳基环氧乙烷。硫化物中的游离基中的游离OH之间的非键相互作用（3，6，和7）和醛的羰基基团控制底物优先在一个特定面上接近基团碳，因此比由甲基保护的羟基化硫化物4产生的叶立德的情况更有效地导致不对称诱导。不能引起这种相互作用。在与甲基保护的羟基硫化物4b和未保护的羟基硫化物3b的催化反应中也观察到相同的相反的不对称诱导。

  DOI：

  10.1021/jo951442+
• 作为产物：
  描述：

  S-甲基 4-甲基苯硫代磺酸酯 、 Lithium; (1R,4R)-1,7,7-trimethyl-bicyclo[2.2.1]hept-2-en-2-olate 以74%的产率得到
  参考文献：
  名称：

  GOODRIDGE, RICHARD J.;HAMBLEY, TREVOR W.;HAYNES, RICHARD K.;RIDLEY, DAMON+, J. ORG. CHEM., 53,(1988) N 13, 2881-2889

  摘要：

  DOI：

文献信息

• Preparation of stable, camphor-derived, optically active allyl and alkyl sulfoxides and thermal epimerization of the allyl sulfoxides
  作者：Richard J. Goodridge、Trevor W. Hambley、Richard K. Haynes、Damon D. Ridley

  DOI：10.1021/jo00248a001

  日期：1988.6
• 1,3-Diselenetanes and 1,3-Dithietanes Derived from Camphor. Formation, Structure, Stereochemistry, and Oxidation to Selenoxide and Sulfoxide Products
  作者：Thomas G. Back、Brian P. Dyck、Masood Parvez

  DOI：10.1021/jo00108a038

  日期：1995.2

  The reaction of camphor enolate with elemental selenium, followed by aerial oxidation, afforded chiefly the endo,endo-dicamphoryl diselenide 3 and 4 selenide. However, in the presence of methyl iodide, the principal products were the syn- and anti-1,3-diselenetanes 5 and 6, formed by the dimerization of the putative selenoketone intermediate 12. The products 5 and 6 were also obtained by the base-catalyzed elimination of HCN from the camphoryl selenocyanate 14, followed by dimerization of the same intermediate 12. The reaction of camphor enolate with sulfur and methyl iodide did not produce the corresponding 1,3-dithietanes, but mainly a mixture of dicamphoryl sulfide and camphoryl methyl sulfide stereoisomers 15-18. Base-catalyzed elimination of camphoryl thiocyanate 19 afforded the anti-1,3-dithietane 21 as the sole stereoisomer via thioketone 20. Oxidation of 21 with PhICl(2) produced a single sulfoxide isomer 24. Further oxidation of the latter with m-CPBA gave a mixture of bis-sulfoxides 25 and 26 and trioxide 27, while exhaustive oxidation of 21 gave the bis-sulfone 29. Treatment of the syn-1,3-diselenetane 5 with PhICl(2) resulted in oxidation of the endo and exo selenium atoms to afford selenoxides 30 and 31 in the ratio of 91:9, respectively. Similar oxidation of the anti isomer 6 produced the selenoxide 32 and a smaller amount of 30 by ring opening and reclosure. X-ray crystal structures of the anti-1,3-diselenetane and -dithietane 6 and 21 were determined.