4,5-cis-2,4,5-triphenyl-1,3-dioxolane | 713095-48-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 4,5-cis-2,4,5-triphenyl-1,3-dioxolane
• 英文别名: meso-2,4,5-triphenyl-1,3-dioxolane；2,4r,5c-Triphenyl-(1.3)-dioxolan；(4R,5S)-2,4,5-triphenyl-1,3-dioxolane
• CAS: 713095-48-8
• 化学式: C₂₁H₁₈O₂
• 分子量: 302.373
• InChiKey: MNNXGJAEKIFJBV-WCRBZPEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,5-cis-2,4,5-triphenyl-1,3-dioxolane 在 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以96%的产率得到(1S,2R)-1,2-diphenylethane-1,2-diol
  参考文献：
  名称：

  4-（叔丁基二甲基甲硅烷氧基）亚苄基乙缩醛：1,2-二醇的新型亚苄基型保护基

  摘要：

  已经开发出一种新的1，2-二醇保护基，对甲硅烷基氧苄叉基。除了逐步脱保护的条件（包括脱甲硅烷基化以及随后在AcOH-THF-H 2 O中对羟基苯亚甲基的酸性水解）之外，我们还建立了在碱性条件下[K 2 CO 3（5当量），一锅脱保护， NH 2 OH·HCl（5当量）和CsF（1当量）的MeOH–H 2 O]溶液。

  DOI：

  10.1016/j.tetlet.2004.03.065
• 作为产物：
  描述：

  苯甲醛 在 [Cp₂TiCl*MnCl₂(THF)2*Cp₂TiCl] 三甲基氯硅烷 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 4,5-cis-2,4,5-triphenyl-1,3-dioxolane 、 r-2,c-4,t-5-triphenyl-1,3-dioxolane
  参考文献：
  名称：

  Catalyst structural effects in titanocene-catalyzed pinacol coupling: activity, stereoselectivity and mechanistic implications

  摘要：

  The effects of catalyst structural variation on the activity and selectivity of titanocene-catalyzed pinacol coupling of cyclohexane carboxaldehyde by Mn/TMSCl have been evaluated. Complexes which have been tested include: Cp2TiCl2 (1), Cp2TiBr2 (2), (C5Me5)(2)TiCl2 (3), (1,3-t-Bu2C5H3)(2)TiCl2 (4), (1,3-t-Bu2C5H3)(Cp)TiCl2 (5), ansa-[(eta (5)-tetrahydroindenyl)CH2CH2(eta (5)-tetrahydroindenyl)]TiCl2 (6), and ansa-[(eta (5)-Cp)CH2CH2(eta (5)-fluorenyl)]TiCl2 (7). Cp2TiCl2 (1) is the most active (pre)catalyst for pinacol silylether (8a) formation, but Brintzinger's complex 6 provides the best DL/meso diastereoselectivity (5:1). Complexes 2, 4 and 7 slowly catalyze the predominant formation of the corresponding pinacol acetal 9a as a secondary product. Comparative stoichiometric reactions of benzaldehyde/Me3SiCl with [Cp2TiCl . -MnCl2(THF)(2). Cp2TiCl] (10) and [Cp2TiCl](2) (11) result in highly diastereoselective pinacol silylether formation with binuclear 11 (29:1), but primarily the production of pinacol acetal (9b) from trimetallic 10, suggesting a dominant role for the binuclear complex (or derived mononuclear species) in the catalytic systems employing Cp2TiCl2/M/TMSCl, contrary to previous suggestions. (C) 2001 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)00892-0

文献信息

• A highly dl-stereoselective pinacolization of aromatic aldehydes mediated by titanium trichloride in dichloromethane
  作者：Angelo Clerici、Laura Clerici、Ombretta Porta

  DOI：10.1016/0040-4039(96)00462-5

  日期：1996.4

  Aromatic aldehydes are stereoselectively coupled to dl-hydrobenzoins on treatment with anhydrous TiCl3/CH2Cl2 solution at room temperature. The observed stereochemistry is briefly discussed in term of Ti(IV)-bridging control.

  在室温下用无水TiCl 3 / CH 2 Cl 2溶液处理时，将芳香醛立体选择性地偶联至dl-氢安息香素。根据Ti（IV）桥联控制简要讨论了观察到的立体化学。
• Glass, Beverley D.; Goosen, Andre; McCleland, Cedric W., Journal of the Chemical Society. Perkin transactions II, 1993, # 11, p. 2175 - 2182
  作者：Glass, Beverley D.、Goosen, Andre、McCleland, Cedric W.

  DOI：——

  日期：——
• 4-(tert-Butyldimethylsilyloxy)benzylidene acetal: a novel benzylidene-type protecting group for 1,2-diols
  作者：Yosuke Kaburagi、Hiroyuki Osajima、Kousei Shimada、Hidetoshi Tokuyama、Tohru Fukuyama

  DOI：10.1016/j.tetlet.2004.03.065

  日期：2004.5

  A novel 1,2-diol-protecting group, p-silyloxybenzylidene group, has been developed. In addition to the stepwise deprotection conditions including desilylation and the subsequent acidic hydrolysis of the p-hydroxybenzylidene group in AcOH–THF–H2O, we have established the one-pot deprotection under basic conditions [K2CO3 (5 equiv), NH2OH·HCl (5 equiv), and CsF (1 equiv) in MeOH–H2O].

  已经开发出一种新的1，2-二醇保护基，对甲硅烷基氧苄叉基。除了逐步脱保护的条件（包括脱甲硅烷基化以及随后在AcOH-THF-H 2 O中对羟基苯亚甲基的酸性水解）之外，我们还建立了在碱性条件下[K 2 CO 3（5当量），一锅脱保护， NH 2 OH·HCl（5当量）和CsF（1当量）的MeOH–H 2 O]溶液。
• Catalyst structural effects in titanocene-catalyzed pinacol coupling: activity, stereoselectivity and mechanistic implications
  作者：Melinda S Dunlap、Kenneth M Nicholas

  DOI：10.1016/s0022-328x(01)00892-0

  日期：2001.7

  The effects of catalyst structural variation on the activity and selectivity of titanocene-catalyzed pinacol coupling of cyclohexane carboxaldehyde by Mn/TMSCl have been evaluated. Complexes which have been tested include: Cp2TiCl2 (1), Cp2TiBr2 (2), (C5Me5)(2)TiCl2 (3), (1,3-t-Bu2C5H3)(2)TiCl2 (4), (1,3-t-Bu2C5H3)(Cp)TiCl2 (5), ansa-[(eta (5)-tetrahydroindenyl)CH2CH2(eta (5)-tetrahydroindenyl)]TiCl2 (6), and ansa-[(eta (5)-Cp)CH2CH2(eta (5)-fluorenyl)]TiCl2 (7). Cp2TiCl2 (1) is the most active (pre)catalyst for pinacol silylether (8a) formation, but Brintzinger's complex 6 provides the best DL/meso diastereoselectivity (5:1). Complexes 2, 4 and 7 slowly catalyze the predominant formation of the corresponding pinacol acetal 9a as a secondary product. Comparative stoichiometric reactions of benzaldehyde/Me3SiCl with [Cp2TiCl . -MnCl2(THF)(2). Cp2TiCl] (10) and [Cp2TiCl](2) (11) result in highly diastereoselective pinacol silylether formation with binuclear 11 (29:1), but primarily the production of pinacol acetal (9b) from trimetallic 10, suggesting a dominant role for the binuclear complex (or derived mononuclear species) in the catalytic systems employing Cp2TiCl2/M/TMSCl, contrary to previous suggestions. (C) 2001 Elsevier Science B.V. All rights reserved.