(S)-3-methyl-2-((phenylsulfonyl)methyl)butan-1-ol | 152549-60-5

• 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: (S)-3-methyl-2-((phenylsulfonyl)methyl)butan-1-ol
• 英文别名: (2S)-3-Methyl-2-[(phenylsulfonyl)methyl]-1-butanol；(2S)-2-(benzenesulfonylmethyl)-3-methylbutan-1-ol
• CAS: 152549-60-5
• 化学式: C₁₂H₁₈O₃S
• 分子量: 242.339
• InChiKey: OXWMCENISSXJOA-NSHDSACASA-N

物化性质

• 沸点：
  419.2±37.0 °C(Predicted)
• 密度：
  1.143±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  62.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-3-methyl-2-((phenylsulfonyl)methyl)butan-1-ol 在 Lindlar's catalyst 吡啶 、 盐酸 、 disodium hydrogenphosphate 、 正丁基锂 、 四丙基高钌酸铵 、 sodium amalgam 、 环己烷 、 4 A molecular sieve 、 氢气 、 碘 、 caesium carbonate 、 戴斯-马丁氧化剂 、 N-甲基吗啉氧化物 、 N,N-二异丙基乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 二甲基亚砜 、 异丙醇 、 丙酮 为溶剂， 反应 106.25h， 生成 (+)-chatancin
  参考文献：
  名称：

  吡喃环戊二烯-diels-alder方法合成（+）-茶霉素：仿生不对称全合成。

  摘要：

  通过原位生成的大环吡喃并pseudo假碱基的跨环Diels-Alder（TADA）反应，实现了（+）-茶霉素的不对称全合成。提出的途径构成了涉及TADA反应的两个拟议的生物合成途径中的第二个。它在生物上将二萜与大麻素联系起来。还概述了一组TADA选择规则，该规则合理地确定了从4个2-羟基-2H-吡喃自行车的动态平衡及其16个可能的TADA过渡态形成（+）-茶豆素的过程。除TADA反应外，合成工作的重点还包括从（S）-香茅醇中组装手性无环大环化底物，以及通过β-酮磺酰氧基/烯酮迈克尔加成反应进行有效的大环化。

  DOI：

  10.1021/jo035193y
• 作为产物：
  描述：

  氯甲基苯硫醚 在 4-二甲氨基吡啶 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 苯亚硒酸 、 双氧水 、 三乙胺 、 zinc dibromide 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 134.0h， 生成 (S)-3-methyl-2-((phenylsulfonyl)methyl)butan-1-ol
  参考文献：
  名称：

  An enzyme-based synthesis of (S)-(−)-3-methyl-2-[(phenylsiilfonyl)-methyl]butyl phenyl sulfide and the stereochemical course of its alkylation

  摘要：

  The two title reactions have been explored. In the first instance, best results were achieved if the chloroacetate ester of 3-methyl-2[(phenylsulfonyl)methyl]-1-butanol was subjected to enzymatic hydrolysis with lipase P30 (Amano). Subsequent conversion to the sulfide of high optical purity (approximately 95% e.e.) was accomplished by means of tri-n-butylphosphine and diphenyl disulfide. The alkylation of this difunctional intermediate with several electrophiles has proven to be rather impressively diastereoselective. The relative (and absolute) course of these transformations has been established by means of X-ray crystallographic and NMR methods and is rationalized at the mechanistic level.

  DOI：

  10.1016/s0957-4166(00)80137-8

文献信息

• Enantioselective Formal α-Methylation and α-Benzylation of Aldehydes by Means of Photo-organocatalysis
  作者：Giacomo Filippini、Mattia Silvi、Paolo Melchiorre

  DOI：10.1002/anie.201612045

  日期：2017.4.10

  photoexcitation of enamines to trigger the formation of reactive carbon-centered radicals from iodosulfones, while the ground-state chiral enamines provide effective stereochemical control over the radical trapping process. The phenylsulfonyl moiety, acting as a redox auxiliary group, facilitates the generation of radicals. In addition, it can eventually be removed under mild reducing conditions to reveal methyl

  本文详细描述了醛与(苯磺酰基)烷基碘的光化学有机催化对映选择性α-烷基化。该化学依赖于烯胺的直接光激发来触发碘砜形成以碳为中心的反应性自由基，而基态手性烯胺则对自由基捕获过程提供有效的立体化学控制。苯磺酰基部分作为氧化还原辅助基团，促进自由基的产生。此外，它最终可以在温和的还原条件下被去除，以露出甲基和苄基。
• Syntheses of thunbergols and α- and β-cembra-2,7,11-triene-4,6-diols
  作者：Peter C. Astles、Eric J. Thomas

  DOI：10.1039/a606551a

  日期：——

  Alkylation of the racemic sulfone 25, available from the epoxide 8, using the iodide 24 followed by reduction gives the protected hydroxy acetal 27. Selective deprotection gives the alcohol 28. This is converted into the bromide 29 which is used to alkylate the keto phosphonate 33. Hydrolysis of the alkylated keto phosphonate 30 gives the aldehyde 31 which is cyclised under mild conditions (63%) and the product treated with methylmagnesium iodide, to give the racemic thunbergols 3 and 4, in a ratio of 3∶4 = 10∶90. The laevorotatory sulfone 25 has been prepared by regioselective ring-opening of the epoxide 38 followed by hydrogenation, selective protection and functional group modification. After alkylation of this sulfone using the iodide 24 and conversion into the aldehyde 46, an asymmetric aldol condensation gives the hydroxy amide 47 which is converted directly into the hydroxy keto phosphonate 49 by reaction with an excess of lithiated dimethyl methylphosphonate. After protection of the hydroxy group, selective hydrolysis of the acetal gives the aldehyde 51 which is cyclised as before to give the naturally occurring cembratrienediols 1 and 2 after reaction with methylmagnesium iodide and deprotection.

  使用碘化物 24 对环氧化物 8 生成的外消旋砜 25 进行烷基化，然后还原，得到受保护的羟基缩醛 27。选择性脱保护得到醇 28。再将其转化为溴化物 29，用于烷基化酮基膦酸酯 33。烷基化的酮基膦酸盐 30 经水解后得到醛 31，醛 31 在温和条件下进行环化（63%），产物经甲基碘化镁处理后得到外消旋噻吩伯醇 3 和 4，比例为 3â¶4 = 10â¶90。通过环氧化物 38 的区域选择性开环，然后进行氢化、选择性保护和官能团修饰，制备出了来沃托砜 25。使用碘化物 24 将该砜烷基化并转化成醛 46 后，通过不对称醛醇缩合得到羟基酰胺 47，再通过与过量的甲基膦酸二甲酯反应直接转化成羟基酮膦酸盐 49。在保护羟基后，选择性水解缩醛得到醛 51，醛 51 与甲基碘化镁反应并脱保护后，如前环化，得到天然的 cembratrienediols 1 和 2。
• Pyranophane Transannular Diels−Alder Approach to (+)-Chatancin:  A Biomimetic Asymmetric Total Synthesis
  作者：Pierre Soucy、Alexandre L'Heureux、András Toró、Pierre Deslongchamps

  DOI：10.1021/jo035193y

  日期：2003.12.1

  An asymmetric total synthesis of (+)-chatancin was achieved via a transannular Diels-Alder (TADA) reaction of an in situ generated macrocyclic pyranophane pseudobase. The presented route constitutes the second of two proposed biosynthetic pathways that involves a TADA reaction. It links this diterpene biogenetically to the cembranoids. A set of TADA selection rules that rationalize the formation of

  通过原位生成的大环吡喃并pseudo假碱基的跨环Diels-Alder（TADA）反应，实现了（+）-茶霉素的不对称全合成。提出的途径构成了涉及TADA反应的两个拟议的生物合成途径中的第二个。它在生物上将二萜与大麻素联系起来。还概述了一组TADA选择规则，该规则合理地确定了从4个2-羟基-2H-吡喃自行车的动态平衡及其16个可能的TADA过渡态形成（+）-茶豆素的过程。除TADA反应外，合成工作的重点还包括从（S）-香茅醇中组装手性无环大环化底物，以及通过β-酮磺酰氧基/烯酮迈克尔加成反应进行有效的大环化。
• An enzyme-based synthesis of (S)-(−)-3-methyl-2-[(phenylsiilfonyl)-methyl]butyl phenyl sulfide and the stereochemical course of its alkylation
  作者：Ronan Guevel、Leo A. Paquette

  DOI：10.1016/s0957-4166(00)80137-8

  日期：1993.5

  The two title reactions have been explored. In the first instance, best results were achieved if the chloroacetate ester of 3-methyl-2[(phenylsulfonyl)methyl]-1-butanol was subjected to enzymatic hydrolysis with lipase P30 (Amano). Subsequent conversion to the sulfide of high optical purity (approximately 95% e.e.) was accomplished by means of tri-n-butylphosphine and diphenyl disulfide. The alkylation of this difunctional intermediate with several electrophiles has proven to be rather impressively diastereoselective. The relative (and absolute) course of these transformations has been established by means of X-ray crystallographic and NMR methods and is rationalized at the mechanistic level.