(R)-3-dodecanol | 581107-05-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (R)-3-dodecanol
• 英文别名: (3R)-Dodecan-3-OL；(3R)-dodecan-3-ol
• CAS: 581107-05-3
• 化学式: C₁₂H₂₆O
• 分子量: 186.338
• InChiKey: OKDGZLITBCRLLJ-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  13
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  癸醛 、 diethylzinc 在 2,2'-dihydroxy-1,1'-binaphthalene-3,3'-bis-diphenylphosphine oxide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 12.0h， 生成 (S)-3-dodecanol 、 (R)-3-dodecanol
  参考文献：
  名称：

  3,3'-Diphosphoryl-1,1'-bi-2-naphthol-Zn（II）配合物作为共轭酸碱催化剂，用于醛的对映选择性二烷基锌

  摘要：

  基于共轭路易斯酸-路易斯碱催化，开发了对一系列芳族，脂族和杂芳族醛（5）的高对映选择性二烷基锌（R 2 2 Zn）。带有氧化膦[P（O）R 2 ]（7），膦酸酯[P（O）（OR）2 ]（8和9）或磷酰胺[P（O）（NR 2）2 ]（10的双功能BINOL配体）通过使用磷酸化-弗里斯重排作为关键步骤来制备3,3'-位。NaphO-Zn（II）-R 2的配位中心以路易斯酸为底物上的羰基，并在3,3'-二磷酰基-BINOL-Zn（II）中以磷酰基（PO）为路易斯碱活化R 2 2 Zn（II）催化剂可以以高对映选择性（高达> 99％ee）促进碳-碳键的形成。通过X射线分析游离配体（7）和四核Zn（II）团簇（21）进行了机理研究，对Zn（II）配合物进行31 P NMR实验，在配体之间没有非线性效应（7））和苯甲醛的Et加合物，以及与某些手性或非手性Zn（II）配合物的化学计量反应，提出了一种包含单体活性中间体的过渡态组装体。

  DOI：

  10.1021/jo060908t

文献信息

• Enantioselective Addition of Organozinc Reagents to Aldehydes Catalyzed by 3,3′-Bis(diphenylphosphinoyl)-BINOL
  作者：Manabu Hatano、Takashi Miyamoto、Kazuaki Ishihara

  DOI：10.1002/adsc.200505221

  日期：2005.10

  The enantioselective addition of organozinc reagents to aromatic and aliphatic aldehydes 1 gives secondary alcohols 2 with excellent enantioselectivities in high yields through the catalytic use of (R)-3,3′-bis(diphenylphosphinoyl)-BINOL (3) or (R)-3,3′-bis(diphenylthiophosphinoyl)-BINOL (4) without Ti(IV) complexes. The coordination of the O or S atom of a (thio)phosphinoyl group bearing a BINOL backbone

  通过对（R）-3,3'-双（二苯基膦酰基）-BINOL（3）或（R）-的催化使用，将有机锌试剂对映选择性地添加到芳族和脂族醛1中，从而以高收率获得具有优异对映选择性的仲醇2。没有Ti（IV）配合物的3，3′-双（二苯基硫代膦酰基）-BINOL（4）。带有BINOL骨架的（硫代）膦酰基的O或S原子与有机锌试剂的配位可以有效地提高有机锌试剂的亲核性。
• Chiral bis(amino alcohol)oxalamides as ligands for asymmetric catalysis. Ti(IV) catalyzed enantioselective addition of diethylzinc to aldehydes
  作者：Gonzalo Blay、Isabel Fernández、Alícia Marco-Aleixandre、José R. Pedro

  DOI：10.1016/j.tetasy.2005.01.039

  日期：2005.3

  Several chiral bis(aminoalcohol)oxalamides with C2-symmetry have been prepared and used as ligands for the enantioselective addition of diethylzinc to aromatic and aliphatic aldehydes. The reaction proceeds in the presence of titanium isopropoxide to give the corresponding (S)-alcohols with ee up to 78%. In the absence of Ti(IV), the alcohols with the opposite configuration are obtained.

  已经制备了几种具有C 2对称性的手性双（氨基醇）草酰胺，并用作将二乙基锌对映选择性加成到芳族和脂族醛上的配体。反应在异丙醇钛存在下进行，得到相应的（S）-醇，其ee高达78％。在没有Ti（IV）的情况下，获得具有相反构型的醇。
• A New Cysteine-Derived Ligand as Catalyst for the Addition of Diethylzinc to Aldehydes: The Importance of a ‘Free’ Sulfide Site for Enantioselectivity
  作者：Antonio Braga、Ludger Wessjohann、Elenilson Alves、Claudio Silveira、Gilson Zeni、Helmoz Appelt

  DOI：10.1055/s-2005-861801

  日期：——

  New chiral sulfides and disulfides were synthesized from readily available and inexpensive cysteine by straightforward methods in order to elucidate the relative importance of the various donor atoms (N, O, S) available in free or alkylated form resulting in covalent or dative bonds to the metal, respectively. Their application in the addition of diethylzinc to aldehydes provides secondary alcohols with up to 99% ee, and S-configuration, when catalytic amounts of disulfide ligands with the ability to form an S-Zn bond were used. In contrast to this, benzyl alcohols with the opposite absolute configuration R could be achieved, albeit with decreased yield and enantioselectivity, by the use of alkylated sulfide ligands.

  新型手性硫化物和二硫化物是通过简单的方法从易得且廉价的半胱氨酸合成的，目的是阐明各种供体原子（N、O、S）在游离或烷基化形式下与金属形成共价或配位键的相对重要性。它们在二乙基锌与醛的加成反应中的应用，能够提供高达99% ee的二级醇，并且具有S-构型，当使用具有形成S-Zn键能力的催化量二硫化物配体时。与此相反，通过使用烷基化硫化物配体，可以得到绝对构型为R的苄醇，尽管产率和对映选择性有所降低。
• Synthesis of novel chiral tridentate aminophenol ligands for enantioselective addition of diethylzinc to aldehydes
  作者：Xiao-Feng Yang、Takuji Hirose、Guang-You Zhang

  DOI：10.1016/j.tetasy.2008.06.027

  日期：2008.7

  Novel chiral tridentate aminophenol ligand (S)-3a was obtained by a Mannich-type reaction of cresol, paraformaldehyde, and (S)-1-(2-methoxyphenyl)-2-methylpropan-1-amine followed by a deprotection step. This tridentate aminophenol ligand shows high yield and enantioselectivity in the diethylzinc additions to a broad range of substrates, including alkyl, aryl, and α,β-unsaturated aldehydes.

  通过甲酚，多聚甲醛和（S）-1-（2-甲氧基苯基）-2-甲基丙烷-1-胺的曼尼希型反应，然后进行脱保护步骤，获得了新型手性三齿氨基酚配体（S）-3a。这种三齿氨基苯酚配体在二乙基锌添加到多种底物（包括烷基，芳基和α，β-不饱和醛）中显示出高收率和对映选择性。
• Synthesis of new chiral imidazolidine disulfides derived from l-cystine and their application in the enantioselective addition of diethylzinc to aldehydes
  作者：Antonio L Braga、Fabrı́cio Vargas、Claudio C Silveira、Leandro H de Andrade

  DOI：10.1016/s0040-4039(02)00300-3

  日期：2002.3

  Several chiral imidazolidine disulfides 4a-d derived from L-cystine have been synthesized. These ligands have been applied as chiral catalysts in the asymmetric addition of diethylzinc to aldehydes. The best results were obtained by employing 5 mol%,, of imidazolidine disulfide 4a, and chiral secondary alcohols were obtained in up to 91% e.e. (C) 2002 Elsevier Science Ltd. All rights reserved.