(+/-)-(phenylsulfonyl)(p-tolylsulfinyl)methane | 129083-18-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+/-)-(phenylsulfonyl)(p-tolylsulfinyl)methane
• 英文别名: Phenylsulfonyl-(p-tolylsulfinyl)methane；Phenylsulfonyl p-tolylsulfinylmethane；p-tolylsulfinylmethyl phenyl sulfone；1-(Benzenesulfonylmethylsulfinyl)-4-methylbenzene
• CAS: 129083-18-7
• 化学式: C₁₄H₁₄O₃S₂
• 分子量: 294.395
• InChiKey: JTPGAQJHFLHRPU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  78.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-(phenylsulfonyl)(p-tolylsulfinyl)methane 在 哌啶 、 pyridinium chlorochromate on silica gel 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 5.5h， 生成 (E)-1-(phenylsulfonyl)pent-1-en-3-one
  参考文献：
  名称：

  Lipase-catalyzed kinetic resolution of .gamma.-hydroxy phenyl sulfones

  摘要：

  Lipase PS (from Pseudomonas cepacia) catalyzed the enantioselective transesterification of racemic gamma-hydroxy-alpha,beta-unsaturated phenyl sulfones 1 and their alpha,beta-saturated derivatives 3 with vinyl acetate in an organic solvent (usually (i)Pr2O). Remarkably, in substrates 1 with (E)-stereochemistry, the enantioselectivity of the process was little influenced by the nature of the R chain. Hence, very high enantiomeric ratios (E greater-than-or-equal-to 45) were observed in substrates 1 bearing short (R = Me or Et), long (R = n-Cr6H13 or n-C10H21), bulky (R = (i)Pr), or functionalized R chains. The (R)-enantiomer was the fast-reacting enantiomer in all cases. Concerning the reactivity, the rate of the reaction decreased significantly with an increase in size or length of the R chain (reaction time for 50% conversion from 3.5 to 162 h). Less satisfactory enantioselectivities (E = 5-48) were obtained when the saturated substrates 3 were used instead of the corresponding alpha,beta-unsaturated alcohols 1.

  DOI：

  10.1021/jo00040a028
• 作为产物：
  描述：

  (+/-)-(phenylsulfonyl)(p-tolylsulfenyl)methane 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以99%的产率得到(+/-)-(phenylsulfonyl)(p-tolylsulfinyl)methane
  参考文献：
  名称：

  Stereoselective Synthesis of Polyhydroxylated Indolizidines from γ-Hydroxy α,β-Unsaturated Sulfones

  摘要：

  The polyhydroxylated indolizidines castanospermine and swainsonine as well as some of their stereoisomers are powerful glycosidase inhibitors. An efficient and stereochemically flexible synthesis of racemic 1,7,8-trihydroxylated and 1,6,7,8-tetrahydroxylated indolizidines (castanospermine stereoisomers) from readily available N-substituted gamma-oxygenated alpha,beta-unsaturated sulfones 3 and 4 has been developed. The construction of the bicyclic skeleton of 1-hydroxyindolizidine has been accomplished by intramolecular conjugate addition of the nitrogen moiety of 3 and 4 to the alpha,beta-unsaturated sulfone unit to give the pyrrolidine intermediates 5 and 6, followed by formation of the C(7)-C(8) bond by intramolecular acylation (or alkylation) of the alpha-sulfonyl carbanion. The stereoselectivity of the pyrrolidine synthesis was highly dependent on the bulkiness of the gamma-oxygenated function; thus, the free alcohols gave predominantly cis-pyrrolidines while the OTIPS derivatives led to the trans isomers. After straightforward functional group transformations, the removal of the sulfonyl group at C(8) either by Julia reaction or by basic elimination (depending on the substrate used) afforded the key C(7)C(8) unsaturated indolizidines 10, 22, 30, and 31, whose stereoselective dihydroxylations with OsO4 gave a variety of cis C(1)C(8a) and-trans C(1)C(8a) trihydroxylated and tetrahydroxylated indolizidines, among which (+/-)-1,7-di-epi-castanospermine and (+/-)-1,8-di-epi-castanospermine have been reported for the first time.

  DOI：

  10.1021/jo972167p

文献信息

• endo-Selective Intramolecular Pauson-Khand Reactions ofγ-Oxygenated-α,β-unsaturated Phenylsulfones
  作者：Javier Adrio、Marta Rodríguez Rivero、Juan C. Carretero

  DOI：10.1002/1521-3765(20010601)7:11<2435::aid-chem24350>3.0.co;2-o

  日期：2001.6.1

  evaluation of the chemical and stereochemical scope of the process in comparison with the Pauson-Khand cyclization of non-sulfonylated enynes, its application to the stereoselective preparation of optically pure C6-substituted bicyclo[3.3.0]oct-1-en-3-ones, and the interpretation of the stereochemical outcome are also discussed.

  通过哌啶促进的相应炔醛与苯磺酰基-（对甲苯基亚磺酰基）甲烷的缩合反应，可以很容易地制备出多种包含 γ-氧化-α,β-不饱和苯砜部分的 1,6-烯炔和 1,7-烯炔并进一步保护羟基。尽管关于缺电子烯烃在 Pauson-Khand 反应中不适用的说法经久不衰，但我们报告说，在热和胺 N-氧化物促进的条件下，这些 1-磺酰化烯炔在分子内 Pauson-Khand 反应中是极好的底物。此外，与通常的烯丙基取代烯炔的外选择性 Pauson-Khand 环化相比，这些 1-磺酰化 3-氧化烯炔的反应以中等或高内向选择性发生。
• Stereoselective synthesis of hydroxypyrrolidines and hydroxypiperidines by cyclization of γ-oxygenated-α,β-unsaturated sulfones
  作者：Juan Carlos Carretero、Ramón Gómez Arrayás、Isabel Storch de Gracia

  DOI：10.1016/0040-4039(96)00551-5

  日期：1996.5

  cis and trans 2,3-disubstituted pyrrolidines and piperidines have been prepared stereoselectively by intramolecular conjugate addition of N-substituted γ-oxygenated-α,β-unsaturated phenyl sulfones. The best cis-selectivities were obtained from the alcohols and the best trans-selectivities from the OTIPS derivatives.

  顺式和反式2，3-二取代的吡咯烷和哌啶已通过分子内共轭添加N-取代的γ-氧化的-α，β-不饱和苯基砜而立体制备。从醇获得最佳的顺式选择性，从OTIPS衍生物获得最佳的反式选择性。
• An efficient and stereoselective synthesis of enantiopure 1,2,7-trihydroxylated pyrrolizidines
  作者：Javier de Vicente、Ramón Gómez Arrayás、Juan C. Carretero

  DOI：10.1016/s0040-4039(99)01265-4

  日期：1999.8

  An efficient approach to the stereoselective synthesis of enantiopure 1,2,7-trihydroxylated pyrrolizidines from the readily available optically pure γ-hydroxy-α,β-unsaturated sulfone 2a is described.

  描述了从容易获得的光学纯的γ-羟基-α，β-不饱和砜2a立体选择性合成对映体纯的1,2,7-三羟基吡咯烷酮的有效方法。
• γ-Oxygenated-α,β-unsaturated sulfones in radical cyclizations and cascade processes
  作者：Javier Adrio、Juan C Carretero

  DOI：10.1016/s0040-4020(97)10368-4

  日期：1998.2

  (substrates 1–4) have been prepared. Both 5-hexenyl and 6-heptenyl radicals, generated by reaction of substrates 1–4 with Bu3SnH/AIBN, underwent an efficient cyclization via intramolecular addition to the vinyl sulfone moiety. By introduction of a double bond joined to the oxygen at γ-position, a cascade process based on two sequential radical cyclizations took place, affording highly substituted 2-oxa[3

  制备了多种具有γ-氧化的α，β-不饱和砜结构的自由基前体（底物1-4）。底物1-4与Bu 3 SnH / AIBN的反应产生的5-己烯基和6-庚烯基均通过分子内加成至乙烯基砜部分而进行了有效的环化。通过引入一个在γ位置连接氧的双键，进行了基于两个连续自由基环化的级联过程，得到了高度取代的2-oxa [3.3.0]或9-oxa [4.3.0]双环化合物。
• The Phenylsulfonyl Group as anendo Stereochemical Controller in Intramolecular Pauson–Khand Reactions of 3-Oxygenated 1,6-Enynes
  作者：Javier Adrio、Marta Rodríguez Rivero、Juan C. Carretero

  DOI：10.1002/1521-3773(20000818)39:16<2906::aid-anie2906>3.0.co;2-8

  日期：2000.8.18