endo-α-methylselenocamphor

• 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: endo-α-methylselenocamphor
• 英文别名: 3-(endo-Methylseleno)camphor；(1R,3S,4S)-1,7,7-trimethyl-3-methylselanylbicyclo[2.2.1]heptan-2-one
• 化学式: C₁₁H₁₈OSe
• 分子量: 245.223
• InChiKey: LVXFBMIGNANTKF-FYBVGQRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.55
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  endo-α-methylselenocamphor 在 二异丁基氢化铝 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 以73%的产率得到
  参考文献：
  名称：

  通过手性硒鎓叶立烯高立体选择性合成1,2,3-三取代环丙烷的第一个例子

  摘要：

  通过硒化叶立德开发了一种新的策略，该策略以高收率，极好的非对映选择性和极高的对映选择性（高达> 99％ee）（见方案），以高收率选择性合成了手性1,2,3-三取代环丙烷的三种立体异构体。还提出了不对称环丙烷化的可能途径。

  DOI：

  10.1002/chem.200801936
• 作为产物：
  描述：

  白樟油 以12%的产率得到
  参考文献：
  名称：

  Back Thomas G., Dyck Brian P., Parvez Masood, J. Chem. Soc. Chem. Commun, (1994) N 4, S 515-516

  摘要：

  DOI：

文献信息

• A Simple Zinc-Mediated Preparation of Selenols
  作者：Claudio Santi、Stefano Santoro、Lorenzo Testaferri、Marcello Tiecco

  DOI：10.1055/s-2008-1078408

  日期：2008.6

  Under acidic conditions zinc reduces diselenides to afford selenols, which can be either isolated or treated in situ with alkyl halides to produce alkyl selenides or with epoxides to give β-hydroxyselenides.

  在酸性条件下，锌可将二硒化合物还原为硒醇，这些硒醇既可分离出来，也可就地与烷基卤反应生成烷基硒醚，或与环氧化物反应得到β-羟基硒醚。
• New Camphor-Derived Selenonium Ylides: Enantioselective Synthesis of Chiral Epoxides
  作者：Xin-Liang Li、Yi Wang、Zhi-Zhen Huang

  DOI：10.1071/ch05157

  日期：——

  selenonium salts 3 as the precursors of two new chiral selenonium ylides 4 can be synthesized stereoselectively from natural d-camphor in good yields. It is found that the reaction of the selenonium salt 3b, an aldehyde, and potassium tert-butoxide can take place smoothly in ‘one-pot’ via the formation of selenonium ylide 4b, to give chiral trans-diaryl epoxides 5 in good yields with good diastereoselectivities

  作为两种新的手性硒叶立德 4 的前体的光学纯硒盐 3 可以由天然 d-樟脑以高收率立体选择性合成。发现硒盐 3b、醛和叔丁醇钾的反应可以通过形成硒内鎓 4b 在“一锅”中顺利进行，从而以良好的收率得到手性反式二芳基环氧化物 5良好的非对映选择性和对映选择性。
• Unexpected formation of 1,3-diselenetanes from the reaction of camphor enolate with selenium
  作者：Thomas G. Back、Brian P. Dyck、Masood Parvez

  DOI：10.1039/c39940000515

  日期：——

  The reaction of camphor enolate with selenium in THF affords mainly the corresponding diselenide, whereas a mixture of two isomeric 1,3-diselenetanes–one of which is characterized by X-ray crystallography–is produced in the presence of methyl iodide.

  樟脑烯醇化物与硒在 THF 中反应主要生成相应的二硒化物，而两种异构体 1,3-二硒烷的混合物（其中一种通过 X 射线晶体学表征）是在碘甲烷存在下产生的。
• 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.