(S)-2-amino-1,1-diphenyl-4-(methylthio)-1-butanol | 104354-36-1

• 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)-2-amino-1,1-diphenyl-4-(methylthio)-1-butanol
• 英文别名: (S)-(-)-2-amino-4-methylthio-1,1-diphenylbutanol；(S)-2-amino-1,1-diphenyl-4-methylthio-1-butanol；(S)-2-amino-4-methylthio-1,1-diphenyl-1-butanol；(S)-α,α-diphenylmethioninol；(S)-2-amino-4-methylsulfanyl-1.1-diphenyl-butanol-(1)；(S)-2-Amino-4-methylmercapto-1.1-diphenyl-butanol-(1)；(2S)-2-amino-4-methylsulfanyl-1,1-diphenylbutan-1-ol
• CAS: 104354-36-1
• 化学式: C₁₇H₂₁NOS
• 分子量: 287.426
• InChiKey: GUUZOCJRRWVFKH-INIZCTEOSA-N

物化性质

• 熔点：
  94-96 °C(Solv: ligroine (8032-32-4))
• 沸点：
  480.8±45.0 °C(Predicted)
• 密度：
  1.143±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  71.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-2-amino-1,1-diphenyl-4-(methylthio)-1-butanol 在 溶剂黄146 、 sodium nitrite 作用下， 生成 (+)-4-methylsulfanyl-1.2-diphenyl-butanone-(1)
  参考文献：
  名称：

  Kanao; Kagami, Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1944, vol. 64, # 3, p. 144

  摘要：

  DOI：
• 作为产物：
  描述：

  L-蛋氨酸 在 盐酸 、 sodium hydroxide 、 氯化亚砜 、 三乙胺 作用下， 以 乙醚 为溶剂， 反应 18.0h， 生成 (S)-2-amino-1,1-diphenyl-4-(methylthio)-1-butanol
  参考文献：
  名称：

  Sulfur-containing β-amino alcohols as catalysts in enantioselective synthesis

  摘要：

  Oxazaborolidine catalysts generated in situ from cyclic or acyclic sulfur containing (R)-cysteine, (S)-penicillamine and (S)-methionine derivates and BH3 have been applied successfully to the enantiocontrolled, catalytic reduction of aromatic ketones. The corresponding sec alcohols could be obtained in excellent enantiomeric excess, up to 100% ee. Using these chiral auxiliaries in the enantioselective addition of diethylzinc to aldehydes afforded optically active sec alcohols in enantiomeric excess up to 93% ee. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00193-6
• 作为试剂：
  描述：

  苯乙酮 在 硼烷四氢呋喃络合物 、 (S)-2-amino-1,1-diphenyl-4-(methylthio)-1-butanol 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 (S)-(-)-1-苯乙醇 、 (R)-(+)-1-苯基乙醇
  参考文献：
  名称：

  Enantioselective catalytic borane reductions of achiral ketones: Synthesis and application of new chiral β-amino alcohols from L-methionine

  摘要：

  The in situ formed chiral oxazaborolidine catalysts from optically active beta-amino alcohols 1-3 from L-methionine ethyl carboxylate 4 have been used successfully in the enantioselective catalytic homogenous borane reductions of various aromatic ketones. The corresponding optically active alcohols are obtained in high optical purity (up to 100% ee).

  DOI：

  10.1016/s0957-4166(00)82245-4

文献信息

• Asymmetric synthesis using chirally modified borohydrides. Part 3. Enantioselective reduction of ketones and oxime ethers with reagents prepared from borane and chiral amino alcohols
  作者：Shinichi Itsuno、Michio Nakano、Koji Miyazaki、Hirofumi Masuda、Koichi Ito、Akira Hirao、Seiichi Nakahama

  DOI：10.1039/p19850002039

  日期：——

  The asymmetric reduction of aromatic and aliphatic ketones, halogeno ketones, hydroxy ketones, keto esters, and ketone oxime ethers with reagents prepared from borane and chiral amino alcohols has been investigated. When α,α-diphenyl β-amino alcohols, such as (2S,3R)-(–)-2-amino-3-methyl-1,1 -diphenylpentanol (2d), were used as a chiral auxiliary, very high enantioselectivities (ca. 90 % e.e.) were

  研究了由硼烷和手性氨基醇制得的试剂对芳香族和脂肪族酮，卤代酮，羟基酮，酮酯和酮肟醚的不对称还原。当使用（2 S，3 R）-（–）-2-氨基-3-甲基-1,1-二苯基戊醇（2d）等α，α-二苯基β-氨基醇作为手性助剂时在还原各种酮和肟醚时，具有很高的对映选择性（约90％ee）。
• A highly enantio- and diastereoselective direct aldol reaction in aqueous medium catalyzed by thiazolidine-based compounds
  作者：Raoní Scheibler Rambo、Caroline Gross Jacoby、Tiago Lima da Silva、Paulo Henrique Schneider

  DOI：10.1016/j.tetasy.2015.04.010

  日期：2015.7

  enantiopure thiazolidine-based organocatalysts were prepared using a simple synthetic approach and successfully applied in the asymmetric direct aldol reaction between various cyclic ketones and aldehydes in a saturated aqueous medium. The aldol adducts were obtained with excellent enantioselectivity (up to >99% ee) and diastereoselectivity (dr >20:1).

  服用左旋氨基酸作为起始原料，一组新的对映体纯的基于噻唑烷的有机催化剂的使用简单的合成方法制备，并且在各种环状酮和醛之间在饱和含水介质中的非对称直接aldol反应成功应用。具有优异的对映选择性（高达> 99％ee）和非对映选择性（2:1博士> 20），得到羟醛加合物。
• Asymmetric Reduction of Prochiral Ketones with <i>N</i>‐Sulfonylated Amino Alcohols as Catalysts
  作者：Zhongqiang Zhou、Yajing Guo

  DOI：10.1080/00397910701818586

  日期：2008.2.13

  Abstract Novel N‐sulfonylated amino alcohols were synthesized from L‐amino acids and (+)‐camphor, and their application to asymmetric reduction of prochiral ketones with NaBH4–BF3 · Et2O is described.

  摘要 由 L-氨基酸和 (+)-樟脑合成了新型 N-磺酰化氨基醇，并描述了它们在 NaBH4-BF3·Et2O 不对称还原前手性酮中的应用。
• Synthesis of chiral tridentate oxazolines with thioether and heteroaryl donor groups and their application in the catalysis of asymmetric Michael reactions
  作者：Jens Christoffers、Alexander Mann、Joachim Pickardt

  DOI：10.1016/s0040-4020(99)00235-5

  日期：1999.4

  Four chiral amino alcohols 1 derived from the natural α-amino acids L-cysteine and L-methionine have been converted with 2-thiophene and 2-pyridine carboxylic acid derivatives 2 to give eight tridentate oxazoline ligands 3a-d and 4a-d with a heteroaryl and a thioether donor function. In one case the coordination geometry at copper(II) was established by X-ray single crystal structure analysis. All

  衍生自天然α-氨基酸L-半胱氨酸和L-蛋氨酸的四种手性氨基醇1已被2-噻吩和2-吡啶羧酸衍生物2转化为八个三齿恶唑啉配体3a-d和4a-d，杂芳基和硫醚供体的功能。在一种情况下，通过X射线单晶结构分析确定了铜（II）的配位几何。关于β-酮酯6与甲基乙烯基酮（7）的迈克尔反应的不对称催化作用，已经用13种金属化合物8筛选了所有配体，得到的最佳结果为19％ee。
• New Chiral Catalysts ContainingN,O-Heterocycles Derived from Chiral Amino Alcohols
  作者：Olga Juanes、Juan Carlos Rodriguez-Ubis、Ernesto Brunet、Helmut Pennemann、Michael Kossenjans、Jürgen Martens

  DOI：10.1002/(sici)1099-0690(199912)1999:12<3323::aid-ejoc3323>3.0.co;2-w

  日期：1999.12

  a new series of chiral catalysts containing N,O-heterocycles of different sizes has been checked in the addition of diethylzinc to benzaldehyde, which was used as a model reaction. The catalysts were derived from natural amino acids, following a relatively simple procedure, and in several cases excellent ee values were obtained. The results were complementary since ee's ranged from 98% (R) to 94% (S)

  在将二乙基锌添加到苯甲醛中时，已检查了一系列新的含有不同尺寸 N,O-杂环的手性催化剂所发挥的对映选择性，苯甲醛用作模型反应。催化剂来源于天然氨基酸，遵循相对简单的程序，在一些情况下获得了极好的 ee 值。结果是互补的，因为 ee 在最终 1-苯基丙-1-醇的 98% (R) 至 94% (S) 过量范围内。分子力学计算表明，R 醇的产生可以通过类似于 Noyori 描述的机制来解释，其中 ZnEt2 仅与 N-C-C-OH 片段相互作用，而 S 对映异构体的形成需要直接亲本氨基酸的侧链和 N,O-杂环的参与。