allyl (5-fluoroadamantylidene)methyl sulfoxide | 140902-98-3

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: allyl (5-fluoroadamantylidene)methyl sulfoxide
• 英文别名: RS-allyl (5-fluoroadamantylidene)methyl sulfoxide；RR-allyl (5-fluoroadamantylidene)methyl sulfoxide
• CAS: 140902-98-3
• 化学式: C₁₄H₁₉FOS
• 分子量: 254.369
• InChiKey: GVFQZESVZUZPEN-LCYFTJDESA-N

反应信息

• 作为反应物：
  描述：

  allyl (5-fluoroadamantylidene)methyl sulfoxide 以 氘代乙腈 为溶剂， 生成 、
  参考文献：
  名称：

  Electronic control of face selection in the [3,3] sigmatropic rearrangement of allyl vinyl sulfoxides

  摘要：

  A study has been made of the thermal rearrangement of adamantylidenemethyl allyl sulfoxide 4 as well as of the racemic RR,SS and RS,SR 5-fluoro diastereomers 8 at 80-degrees-C. The parent compound 4 initially gives a mixture of the (E)- and (Z)-sulfines 5; the E product subsequently isomerizes, more slowly but completely, to the Z compound. Under the same conditions, mixtures of the diastereomers 8 produce mixtures of four mesoforms, two of which ((EE)- and (ZE)-9) subsequently rearrange further to the other two ((EZ)- and (ZZ)-9). The configurations of the starting materials and products were determined by NMR methods. A study of the rates of these various processes made it possible to define the compositions of the sulfine mixtures that form initially from sulfoxides 8. The conclusion is that both a steric and an electronic effect are operating simultaneously to influence the stereochemistry. The steric effect is a response to the need to avoid axial oxygen in the pseudo-chair transition state; the electronic effect favors the formation of a CC bond antiperiplanar to the more electron-rich vicinal bonds. As was the case in the oxy-Cope reaction studied earlier, the steric effect is the larger of the two by a small margin.

  DOI：

  10.1021/jo00037a031