(-)-5-<(tert-butyl-dimethyl-silyl)-oxy>-1-phenyl-pentan-1-ol | 158197-45-6

• 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: (-)-5-<(tert-butyl-dimethyl-silyl)-oxy>-1-phenyl-pentan-1-ol
• 英文别名: (S)-5-(tert-butyldimethylsiloxy)-1-phenyl-1-pentanol；(S)-5-(tert-butyl-dimethyl-silanyloxy)-1-phenyl-pentan-1-ol；(1S)-5-[tert-butyl(dimethyl)silyl]oxy-1-phenylpentan-1-ol
• CAS: 158197-45-6
• 化学式: C₁₇H₃₀O₂Si
• 分子量: 294.51
• InChiKey: WNAQMXXAPOQNBT-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.91
• 重原子数：
  20.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  甲氧基-三氟甲基苯 、 (-)-5-<(tert-butyl-dimethyl-silyl)-oxy>-1-phenyl-pentan-1-ol 在 4-二甲氨基吡啶 作用下， 以 氯仿 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  Ti-TADDOLate-catalyzed, highly enantioselective addition of alkyl- and aryl-titanum derivatives to aldehydes

  摘要：

  Toluene-ether or toluene-hexane solutions of aryl and alkyl triisopropoxy titanium reagents (free of Li, Mg, or Zn salts) are prepared from the corresponding Li or Grignard reagents and ClTi((OPr)-Pr-i)(3), with careful removal of salts (centrifugation of LiCl or of dioxane.MgX(2), and addition of 12-crown-4). The solutions of the organotitanium compounds are combined with one equiv. of an aldehyde and 0.2 equiv. of (R,R)-diisopropoxy-(alpha,alpha,alpha',alpha'-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4,5-dimethanolato) titanium (Ti-TADDOLate 3) at dry-ice temperature. Warming up to room temperature leads to nucleophilic addition to the (Si)-face of the aldehydes with enantioselectivities as high as 99.5 : 0.5 (products 4 - 33 in Scheme 4). Functional groups or protecting groups and branching in the Ti-R group and in the aldehyde must be remote from the reacting centers. Aryl groups can be added to aldehydes by this method. - In contrast to all the enantioselective R(2)Zn additions to aldehydes, in which only one R-group is actually transferred, a twice as economic use is made of the originally employed R-metal reagent in the method described here. - A procedure for multigram preparation of the spiro-Ti-TADDOLate (2) employed for the in situ generation of the catalyst (3) is described, and details of the determination of enantiomer ratios (er) by GC and NMR methods are given (Tab. 2, 3). The mechanistic interpretation of Ti-TADDOLate-mediated nucleophilic additions as derived previously (ref.(4e)) is also compatible with this monometallic variant of the method.

  DOI：

  10.1016/s0040-4020(01)90475-2
• 作为产物：
  描述：

  苯甲醛 、 (3-丁烯-1-基氧基)(二甲基)(2-甲基-2-丙基)硅烷 在 titanium(IV) isopropylate 、 Diethylborane 、 diethylzinc 、 (1R)-反-N,N′-1,2-环己二基双(1,1,1-三氟甲磺酰胺) 作用下， 生成 (-)-5-<(tert-butyl-dimethyl-silyl)-oxy>-1-phenyl-pentan-1-ol
  参考文献：
  名称：

  通过硼锌交换制备功能化的二烷基锌。醛的反应性和催化不对称加成。

  摘要：

  烯烃与Et（2）BH的氢硼化反应生成的二乙基（烷基）硼烷2容易与Et（2）Zn进行硼-锌交换，从而提供了一系列多官能的伯，仲和苄基二有机锌。在CuCN.2LiCl存在下，使所得的二有机锌3与各种亲电试剂（烯丙基卤化物，酰氯，亚烷基丙二酸酯，丙酸乙酯，硝基烯烃）反应，具有极好的收率。用由非对映体纯的二乙基（烷基）硼烷制备的仲二烷基锌，发生硼-锌交换而失去立体化学。在手性催化剂55的存在下，将3-不对称地加成到醛中，提供了光学活性的多官能仲醇（50至超过96％ee）。

  DOI：

  10.1021/jo961129n

文献信息

• Catalytic asymmetric reductive addition of olefins to aldehydes mediated by boron and zinc organometallics
  作者：Lothar Schwink、Paul Knochel

  DOI：10.1016/0040-4039(94)88412-9

  日期：1994.11

  A procedure involving a hydroboration, boron-zinc exchange and asymmetric addition to an aldehyde allows the reductive addition of olefins to aldehydes in 50–96 % ee. A short and efficient 3 step synthesis of ginnol (61 % overall yield, 92 % ee) demonstrates the synthetic utility of the method.

  涉及硼氢化反应，硼锌交换和不对称加成醛的过程，可以使烯烃以50–96％ee还原性加成到醛中。短而有效的三步合成ginnol（61％的总收率，92％ee）证明了该方法的合成效用。
• Catalytic Enantioselective Addition of Organozirconium Reagents to Aldehydes
  作者：Ricard Solà、Marcos Veguillas、María González-Soria、Nicholas Carter、M. Fernández-Ibáñez、Beatriz Maciá

  DOI：10.3390/molecules23040961

  日期：——

  A catalytic enantioselective addition reaction of alkylzirconium species to aromatic aldehydes is reported. The reaction, facilitated by a chiral nonracemic diol ligand complex with Ti(OiPr)4, proceeds under mild and convenient conditions, and no premade organometallic reagents are required since the alkylzirconium nucleophiles are generated in situ by hydrozirconation of alkenes with the Schwartz

  报道了烷基锆物种与芳香醛的催化对映选择性加成反应。该反应由手性非外消旋二醇配体与 Ti(OiPr)4 配合物促进，在温和方便的条件下进行，并且不需要预制的有机金属试剂，因为烷基锆亲核试剂是通过烯烃与 Schwartz 试剂的氢化锆化原位生成的。该方法与功能化亲核试剂和广泛的芳香醛兼容。
• Ti-TADDOLate-catalyzed, highly enantioselective addition of alkyl- and aryl-titanum derivatives to aldehydes
  作者：Beat Weber、Dieter Seebach

  DOI：10.1016/s0040-4020(01)90475-2

  日期：——

  Toluene-ether or toluene-hexane solutions of aryl and alkyl triisopropoxy titanium reagents (free of Li, Mg, or Zn salts) are prepared from the corresponding Li or Grignard reagents and ClTi((OPr)-Pr-i)(3), with careful removal of salts (centrifugation of LiCl or of dioxane.MgX(2), and addition of 12-crown-4). The solutions of the organotitanium compounds are combined with one equiv. of an aldehyde and 0.2 equiv. of (R,R)-diisopropoxy-(alpha,alpha,alpha',alpha'-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4,5-dimethanolato) titanium (Ti-TADDOLate 3) at dry-ice temperature. Warming up to room temperature leads to nucleophilic addition to the (Si)-face of the aldehydes with enantioselectivities as high as 99.5 : 0.5 (products 4 - 33 in Scheme 4). Functional groups or protecting groups and branching in the Ti-R group and in the aldehyde must be remote from the reacting centers. Aryl groups can be added to aldehydes by this method. - In contrast to all the enantioselective R(2)Zn additions to aldehydes, in which only one R-group is actually transferred, a twice as economic use is made of the originally employed R-metal reagent in the method described here. - A procedure for multigram preparation of the spiro-Ti-TADDOLate (2) employed for the in situ generation of the catalyst (3) is described, and details of the determination of enantiomer ratios (er) by GC and NMR methods are given (Tab. 2, 3). The mechanistic interpretation of Ti-TADDOLate-mediated nucleophilic additions as derived previously (ref.(4e)) is also compatible with this monometallic variant of the method.
• Preparation of Functionalized Dialkylzincs via a Boron−Zinc Exchange. Reactivity and Catalytic Asymmetric Addition to Aldehydes
  作者：Falk Langer、Lothar Schwink、Arokiasamy Devasagayaraj、Pierre-Yves Chavant、Paul Knochel

  DOI：10.1021/jo961129n

  日期：1996.11.15

  The hydroboration of olefins with Et(2)BH provides diethyl(alkyl)boranes 2 which readily undergo a boron-zinc exchange with Et(2)Zn providing a range of polyfunctional primary, secondary, and benzylic diorganozincs. The resulting diorganozincs 3 have been reacted with various electrophiles (allylic halides, acid chlorides, alkylidenemalonates, ethyl propiolate, nitroolefins) in the presence of CuCN

  烯烃与Et（2）BH的氢硼化反应生成的二乙基（烷基）硼烷2容易与Et（2）Zn进行硼-锌交换，从而提供了一系列多官能的伯，仲和苄基二有机锌。在CuCN.2LiCl存在下，使所得的二有机锌3与各种亲电试剂（烯丙基卤化物，酰氯，亚烷基丙二酸酯，丙酸乙酯，硝基烯烃）反应，具有极好的收率。用由非对映体纯的二乙基（烷基）硼烷制备的仲二烷基锌，发生硼-锌交换而失去立体化学。在手性催化剂55的存在下，将3-不对称地加成到醛中，提供了光学活性的多官能仲醇（50至超过96％ee）。