2,3-Dimethyl-1-phenylsulfanyl-butan-2-ol | 180078-61-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2,3-Dimethyl-1-phenylsulfanyl-butan-2-ol
• 英文别名: 2,3-Dimethyl-1-phenylsulfanylbutan-2-ol
• CAS: 180078-61-9
• 化学式: C₁₂H₁₈OS
• 分子量: 210.34
• InChiKey: XRRRMYUUPRXRLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  45.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3-Dimethyl-1-phenylsulfanyl-butan-2-ol 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 4.0h， 以2.6 g的产率得到3-甲基-2-[(苯基硫代)甲基]-2-丁烯
  参考文献：
  名称：

  Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines

  摘要：

  Allyl aryl sulfides 1 and 5 were shown to undergo an imidation/[2,3]-sigmatropic rearrangement reaction upon treatment with N-tert-butyloxycarbonyl azide (BocN(3)) and catalytic amounts of FeCl2 in CH2Cl2. The N-Boc-protected N-allyl sulfenamides 3 and 21 were obtained in yields between 48 and 75% (12 examples), Whereas the reaction is well suited for the transformation of alpha-unbranched sulfides to a-branched sulfenamides, the enantiomerically pure alpha-branched sulfides 10 and 13 reacted sluggishly. The corresponding sulfenamides 22 and 23 were obtained in only moderate enantiomeric excess (36-39% eel. A reaction mechanism is proposed that postulates the intermediacy of an N-Boc-substituted Fe(IV)-nitrene complex 14 acting as the imidation reagent in the catalytic cycle. Possible side reactions are discussed. The benzenesulfenamides 3 were further converted into N-Boc-N-allylamines 4 by removal of the phenylsulfanyl group. Bu3SnH in benzene was found to be the reagent of choice for the deprotection of alpha-branched amines that bear a secondary allyl substituent (five examples, 71-93% yield). This method failed for the alpha-branched amines 3i-k with a tertiary allyl substituent. The phenylsulfanyl group was finally removed with P(OEt)(3)/NEt3 in CH2Cl2 (three examples, 43-62% yield).

  DOI：

  10.1021/jo991569p
• 作为产物：
  描述：

  (3,3-二甲基环氧乙烷基)甲醇 在 吡啶 、 三苯基膦 作用下， 以 正己烷 为溶剂， 反应 25.5h， 生成 2,3-Dimethyl-1-phenylsulfanyl-butan-2-ol
  参考文献：
  名称：

  环氧化物的α-亚磺酰基导向的开环反应。1. 与有机铝试剂的高度区域和立体选择性反应及其在聚合信息素合成中的应用

  摘要：

  1-苯硫基-2,3-环氧烷烃与三烷基铝的反应显示出明确的 C-2 亲核开环选择性，并得到完全保留 C-2 构型的 C-2 烷基化产物。相比之下，当与烯基（二烷基）铝、二烷基（炔基）铝或 DIBAL 反应时，亲核攻击发生在 C-1 处，伴随着亚磺基重排到 C-2，在C-2。这些环氧化物的反应被认为是通过环锍离子中间体进行的。在应用本反应后，非洲棕榈象鼻虫的聚集信息素在短步骤中立体选择性地合成。

  DOI：

  10.1246/bcsj.69.2095

文献信息

• Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched <i>N</i>-<i>tert</i>-Butyloxycarbonyl (Boc)-Protected <i>N</i>-Allylamines
  作者：Thorsten Bach、Christina Körber

  DOI：10.1021/jo991569p

  日期：2000.4.1

  Allyl aryl sulfides 1 and 5 were shown to undergo an imidation/[2,3]-sigmatropic rearrangement reaction upon treatment with N-tert-butyloxycarbonyl azide (BocN(3)) and catalytic amounts of FeCl2 in CH2Cl2. The N-Boc-protected N-allyl sulfenamides 3 and 21 were obtained in yields between 48 and 75% (12 examples), Whereas the reaction is well suited for the transformation of alpha-unbranched sulfides to a-branched sulfenamides, the enantiomerically pure alpha-branched sulfides 10 and 13 reacted sluggishly. The corresponding sulfenamides 22 and 23 were obtained in only moderate enantiomeric excess (36-39% eel. A reaction mechanism is proposed that postulates the intermediacy of an N-Boc-substituted Fe(IV)-nitrene complex 14 acting as the imidation reagent in the catalytic cycle. Possible side reactions are discussed. The benzenesulfenamides 3 were further converted into N-Boc-N-allylamines 4 by removal of the phenylsulfanyl group. Bu3SnH in benzene was found to be the reagent of choice for the deprotection of alpha-branched amines that bear a secondary allyl substituent (five examples, 71-93% yield). This method failed for the alpha-branched amines 3i-k with a tertiary allyl substituent. The phenylsulfanyl group was finally removed with P(OEt)(3)/NEt3 in CH2Cl2 (three examples, 43-62% yield).
• <i>α</i>-Sulfenyl-Directed Ring-Opening Reactions of Epoxides. 1. Highly Regio- and Stereoselective Reaction with Organo-Aluminum Reagents and Application to the Synthesis of an Aggregation Pheromone
  作者：Changqing Liu、Yukihiko Hashimoto、Kazuaki Kudo、Kazuhiko Saigo

  DOI：10.1246/bcsj.69.2095

  日期：1996.7

  rearrangement of the sulfenyl group to the C-2 with the complete inversion of the configuration at the C-2. The reactions of these epoxides were considered to proceed via an episulfonium ion intermediate. Upon applying the present reaction, an aggregation pheromone of African Palm Weevil was stereoselectively synthesized in short steps.

  1-苯硫基-2,3-环氧烷烃与三烷基铝的反应显示出明确的 C-2 亲核开环选择性，并得到完全保留 C-2 构型的 C-2 烷基化产物。相比之下，当与烯基（二烷基）铝、二烷基（炔基）铝或 DIBAL 反应时，亲核攻击发生在 C-1 处，伴随着亚磺基重排到 C-2，在C-2。这些环氧化物的反应被认为是通过环锍离子中间体进行的。在应用本反应后，非洲棕榈象鼻虫的聚集信息素在短步骤中立体选择性地合成。