1-hydroxy-2-methyl-1-phenylpentyl 3-benzoate

• 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: 1-hydroxy-2-methyl-1-phenylpentyl 3-benzoate
• 英文别名: (1R,2S,3S)-1-hydroxy-2-methyl-1-phenylpent-3-yl benzoate；1-hydroxy-2-methyl-1-phenylpent-3-yl benzoate；(1R,2R,3S)-2-methyl-1-phenyl-1,3-pentanediol 3-O-benzoate；[(1R,2S,3S)-1-hydroxy-2-methyl-1-phenylpentan-3-yl] benzoate
• 化学式: C₁₉H₂₂O₃
• 分子量: 298.382
• InChiKey: IVTGKNZGOPTZLQ-FHLIZLRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-hydroxy-2-methyl-1-phenylpentyl 3-benzoate 在 正丁基锂 、 (R)-3,3'-二苯基-1,1'-联萘酚 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.0h， 生成 3-hydroxy-2-methyl-1-phenylpentyl benzoate 、 (1S,2S,3R)-3-hydroxy-2-methyl-1-phenylpentyl benzoate
  参考文献：
  名称：

  Direct Enantioselective Aldol−Tishchenko Reaction Catalyzed by Chiral Lithium Diphenylbinaphtholate

  摘要：

  Chiral lithium diphenylbinaphtholate is an effective catalyst for the enantioselective aldol-Tishchenko reaction, affording 1,3-diol derivatives with three contiguous chiral centers and high stereoselectivities. Successive aldol-aldol-Tishchenko reactions gave a triol derivative with five consecutive chiral centers. The present reaction was applicable to highly enantioselective Evans-Tishchenko reduction.

  DOI：

  10.1021/ol103156h
• 作为产物：
  描述：

  苯甲醛 在 正丁基锂 、 (R)-3,3'-二苯基-1,1'-联萘酚 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 6.0h， 生成 1-hydroxy-2-methyl-1-phenylpentyl 3-benzoate 、 1-hydroxy-2-methyl-1-phenylpentyl 3-benzoate
  参考文献：
  名称：

  Direct Enantioselective Aldol−Tishchenko Reaction Catalyzed by Chiral Lithium Diphenylbinaphtholate

  摘要：

  Chiral lithium diphenylbinaphtholate is an effective catalyst for the enantioselective aldol-Tishchenko reaction, affording 1,3-diol derivatives with three contiguous chiral centers and high stereoselectivities. Successive aldol-aldol-Tishchenko reactions gave a triol derivative with five consecutive chiral centers. The present reaction was applicable to highly enantioselective Evans-Tishchenko reduction.

  DOI：

  10.1021/ol103156h

文献信息

• Samarium Ion-Promoted Cross-Aldol Reactions and Tandem Aldol/Evans−Tishchenko Reactions
  作者：Ling Lu、Hung-Yu Chang、Jim-Min Fang

  DOI：10.1021/jo981675b

  日期：1999.2.1

  effective Lewis acids to catalyze tandem aldol/Evans-Tishchenko reactions. The aldol/Evans-Tishchenko reactions of methyl ketones with aldehydes occurred at 0 degrees C to give alpha,gamma-anti diol monoesters 53a-59a. When the reactions were conducted at room temperature, a certain degree of transesterification took place. The aldol/Evans-Tishchenko reactions of ethyl or benzyl ketones with aldehydes

  通过在环境温度下SmI（2）或SmI（3）以及分子筛的催化，可以实现羰基化合物的跨醇醛反应。在与供体底物如丙酮，环戊酮和环己酮的交叉醇醛缩合反应中，可以将1，3-二氯丙酮和1-氯丙酮用作受体底物。与（R）-甘油醛丙酮化物的交叉醛醇缩合反应产生光学纯的化合物25-32，其立体化学与偶极模式的椅子状螯合物过渡态一致。SmI（2）分子筛或SmI（3）分子筛也可作为有效的路易斯酸来催化串联羟醛/埃文斯-季申科反应。甲基酮与醛的aldol / Evans-Tishchenko反应在0℃下发生，得到α，γ-抗二醇单酯53a-59a。当反应在室温下进行时，发生了一定程度的酯交换反应。乙基或苄基酮与醛的aldol / Evans-Tishchenko反应生成α，β-抗-α，γ-抗二醇单酯60a-65a。然而，环状酮与苯甲醛的醛醇/埃文斯-季申科反应以不同的立体选择性发生，得到α，β-syn-α，γ-抗二醇
• Efficient Preparation of 1,3-Diol Derivatives with Three Contiguous Stereocenters by an Enantioselective Direct Aldol–Tishchenko Reaction
  作者：Makoto Nakajima、Tomonori Ichibakase

  DOI：10.1055/s-0031-1291138

  日期：——

  contiguous stereocenters were efficiently prepared by an enantioselective direct aldol–Tishchenko reaction catalyzed by dilithium 3,3′-diphenylbinaphtholate. The reactions of acyclic ketones as aldol donors gave 1,2-syn-1,3-anti-diol derivatives, whereas the reactions of cyclic ketones as aldol donors gave 1,2-anti-1,3-anti-diol derivatives. Sequential aldol–aldol–Tishchenko reactions gave a triol derivative

  摘要 通过3,3'-二苯基联萘二酸二锂催化的对映选择性直接羟醛-Tishchenko反应，可以有效地制备具有三个连续立体中心的1,3-二醇衍生物。无环酮作为醛醇供体的反应得到1,2- syn -1,3-抗二醇衍生物，而环酮作为醛醇供体的反应得到1,2-抗-1,3-抗二醇衍生物。连续的醛醇-醛醇-季申科反应给出了具有五个连续手性中心的三醇衍生物。 通过3,3'-二苯基联萘二酸二锂催化的对映选择性直接羟醛-Tishchenko反应，可以有效地制备具有三个连续立体中心的1,3-二醇衍生物。无环酮作为醛醇供体的反应得到1,2- syn -1,3-抗二醇衍生物，而环酮作为醛醇供体的反应得到1,2-抗-1,3-抗二醇衍生物。连续的醛醇-醛醇-季申科反应给出了具有五个连续手性中心的三醇衍生物。
• Titanium-Mediated Aldol-Tishchenko Reaction: A Stereoselective Synthesis of Differentiated anti 1,3-Diol Monoesters
  作者：Rainer Mahrwald、Burkhard Costisella

  DOI：10.1055/s-1996-4339

  日期：1996.9

  anti 1,3-Diol monoesters were obtained in a high level of stereoselectivity by a one-pot aldol-Tishchenko reaction of ketones with aldehydes using substoichiometric amounts of titanium ate complexes.

  通过酮与醛在亚化学计量量的钛配合物存在下进行的一锅法羟醛缩合-Tishchenko反应，高效地获得了anti 1,3-二醇单酯产物，并展现出高度的立体选择性。
• The first example of a catalytic asymmetric aldol-Tishchenko reaction of aldehydes and aliphatic ketones
  作者：Jacek Mlynarski、Marcin Mitura

  DOI：10.1016/j.tetlet.2004.08.134

  日期：2004.10

  condensation––Evans–Tishchenko reduction of aldehydes and ketones. Chiral ytterbium complexes were found to catalyze the condensation of aromatic aldehydes with 3-pentanone (and other ketones) giving rise to the anti-1,3-diol monoesters in good yield, and with high diastereocontrol and moderate levels of enantioselectivity. Three adjacent stereogenic centers are created in one reaction sequence in acyclic systems

  已经筛选了路易斯酸和手性配体的多种组合，以进行对映选择性的直接串联羟醛缩合反应–埃文斯–季申科还原醛和酮。发现手性配合物催化芳族醛与3-戊酮（和其他酮）的缩合反应，从而以高收率，高非对映异构控制度和中等对映选择性水平产生抗-1,3-二醇单酯。在无环系统的一个反应序列中创建了三个相邻的立体生成中心。
• Chiral Ytterbium Complex-Catalyzed Direct Asymmetric Aldol-Tishchenko Reaction: Synthesis ofanti-1,3-Diols
  作者：Jacek Mlynarski、Bartosz Rakiel、Maciej Stodulski、Agata Suszczyńska、Jadwiga Frelek

  DOI：10.1002/chem.200600357

  日期：2006.10.25

  The asymmetric aldol-Tishchenko reaction of aromatic aldehydes with aliphatic and aromatic ketones has been developed as an efficient strategy for the synthesis of anti-1,3-diols in good yield with high diastereocontrol and good levels of enantioselectivity. This domino-type reaction is catalyzed by a chiral ytterbium complex that promotes both the aldol reaction through enolization of the carbonyl

  已开发出芳族醛与脂族和芳族酮的不对称aldol-Tishchenko反应，这是一种高效合成抗-1,3-二醇的有效策略，具有高非对映异构控制性和良好的对映选择性。这种多米诺型反应是由手性complex配合物催化的，该手性配合物通过羰基化合物的烯醇化和醛醇中间体的埃文斯-季申科还原而促进醛醇反应。还对所得二醇的立体化学进行了研究，并最终通过使用CD技术进行了证明。