(4R,5R)-2,2-Diethyl-α,α,α',α'-tetrakis(3,5-dimethylphenyl)-1,3-dioxolane-4,5-dimethanol | 138710-29-9

• 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: (4R,5R)-2,2-Diethyl-α,α,α',α'-tetrakis(3,5-dimethylphenyl)-1,3-dioxolane-4,5-dimethanol
• 英文别名: ((4R,5R)-2,2-diethyl-1,3-dioxolane-4,5-diyl)bis(bis(3,5-dimethylphenyl)methanol)；[(4R,5R)-2,2-Diethyl-1,3-dioxolane-4,5-diyl]bis[bis(3,5-dimethylphenyl)methanol]；[(4R,5R)-5-[bis(3,5-dimethylphenyl)-hydroxymethyl]-2,2-diethyl-1,3-dioxolan-4-yl]-bis(3,5-dimethylphenyl)methanol
• CAS: 138710-29-9
• 化学式: C₄₁H₅₀O₄
• 分子量: 606.846
• InChiKey: UKBYGTDZHRFSPL-XPSQVAKYSA-N

物化性质

• 沸点：
  711.8±55.0 °C(Predicted)
• 密度：
  1.095±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  45
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R,5R)-2,2-Diethyl-α,α,α',α'-tetrakis(3,5-dimethylphenyl)-1,3-dioxolane-4,5-dimethanol 、 苯基二氯化磷 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以88%的产率得到(3aR,8aR)-4,4,8,8-tetrakis(3,5-dimethylphenyl)-2,2-diethyl-6-phenyltetrahydro[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepine
  参考文献：
  名称：

  Catalytic Enantioselective One-pot Aminoborylation of Aldehydes: A Strategy for Construction of Nonracemic α-Amino Boronates

  摘要：

  We report a strategy for the conversion of aldehydes to enantiomerically enriched alpha-amino boronates through the intermediacy of in situ-generated silylimines. This transformation is brought about by Pt-catalyzed asymmetric addition of B-2(pin)(2) across the imine double bond. An attractive feature of the intermediate diboration adduct is that it can be acylated directly and provides convenient access to important N-acyl alpha-amino boronic ester derivatives.

  DOI：

  10.1021/ja402569j
• 作为产物：
  描述：

  3-戊酮 在 对甲苯磺酸 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成 (4R,5R)-2,2-Diethyl-α,α,α',α'-tetrakis(3,5-dimethylphenyl)-1,3-dioxolane-4,5-dimethanol
  参考文献：
  名称：

  在（RO）2 TiCl 2型对映选择性Diels-Alder反应手性催化剂中π-π吸引相互作用的重要性的证据

  摘要：

  二醇4与Ti（Oi-Pr）4继之以SiCl 4的反应导致形成Ti（IV）配合物5，该配合物是对映选择性Diels-Alder反应非常有效的催化剂。如式7所示，已观察到的高对映选择性（> 95：5）的起源可能在于芳族基团与亲二烯体之间有吸引力的π-π相互作用。

  DOI：

  10.1016/0040-4039(91)80149-z

文献信息

• Pd‐Catalyzed Enantioselective Ring Opening/Cross‐Coupling and Cyclopropanation of Cyclobutanones
  作者：Jian Cao、Ling Chen、Feng‐Na Sun、Yu‐Li Sun、Ke‐Zhi Jiang、Ke‐Fang Yang、Zheng Xu、Li‐Wen Xu

  DOI：10.1002/anie.201813071

  日期：2019.1.14

  A palladium‐catalyzed enantioselective sequential ring‐opening/cross‐coupling of cyclobutanones is disclosed that provides chiral indanones bearing C3‐quaternary stereocenters. The reaction process involves palladium‐catalyzed nucleophilic addition of cyclobutanones and aryl halides, enantioselective β‐carbon elimination, and intermolecular trapping of a transient σ‐alkylpalladium complex with boronic

  公开了钯催化的环丁酮的对映选择性顺序开环/交叉偶联，其提供了带有C3四元立体中心的手性茚满酮。反应过程涉及环丁烯酮和芳基卤化物的钯催化亲核加成，对映选择性β-碳消除以及用硼酸在分子间捕获瞬态σ-烷基钯络合物。或者，在没有外部偶联剂的情况下，通过CH键功能化实现分子内环丙烷化，从而以良好的收率和对映选择性提供手性环丙烷稠合的茚满酮。
• On the Ti-TADDOLate-Catalyzed Diels-Alder Addition of 3-Butenoyl-1,3-oxazolidin-2-one to Cyclopentadiene. General Features of Ti-BINOLate- and Ti-TADDOLate-Mediated Reactions
  作者：Dieter Seebach、Robert Dahinden、Roger E. Marti、Albert K. Beck、Dietmar A. Plattner、Florian N. M. Kuehnle

  DOI：10.1021/jo00111a042

  日期：1995.3

  A systematic investigation of the enantioselective Diels-Alder addition of 3-butenoyl-1,3-oxazolidin-2-one to cyclopentadiene under the influence of catalytic amounts of dichloro-Ti complexes of alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOLs) is described. The influence of the mode of catalyst preparation, amount of catalyst, presence of molecular sieves, concentration of the reactands temperature, solvent, and TADDOL structure on this reaction is studied. Best results (enantiomer ratio er 94:6) are obtained with the TADDOL-bearing Arl = C6H5 and C6H5/CH3 substituents in the dioxolane 2-position (47) and with the C-2-symmetrical TADDOL with Arl = 2-naphthyl and two CH3 groups on the dioxolane 2-position (16). A surprising reversal of the absolute topicity of the reaction is observed with TADDOLs (15, 28, 32, 38) bearing four 1-naphthyl groups: the 2(R)- instead of the 2(S)-bicyclo[2.2.1]hept-5-en-2-carboxylic acid derivatives are formed with enantioselectivities of up to 86:14. The crystal structures of several TADDOLs (16, 28, 47) and of the tetracyclohexylanalog 50 are described and compared with previously determined structures. A superposition of 29 structures reveals that the cyclic array of atoms of the TADDOLate moiety always has two axial and two equatorial aryl groups in a lambda-type conformation when derived from (RP)-tartrate and in a delta-type conformation when derived from(S,S)-tartrate. The binaphthols (BINOLs) show similar structural features (lambda in (P) or (S) and delta in (M) or (R) enantiomers). A mnemonic rule is disclosed which applies to the steric course of Ti-BINOLate- and Ti-TADDOLate-mediated reactions involving monodentate and bidentate electrophiles. The possible structure of the reactive complex involved in enantioselective reactions mediated by Ti-BINOLates and -TADDOLates, i.e., inter- and intramolecular [2 + 2] and [4 + 2] cycloadditions and ene reactions, is discussed.
• Catalytic Enantioselective One-pot Aminoborylation of Aldehydes: A Strategy for Construction of Nonracemic α-Amino Boronates
  作者：Kai Hong、James P. Morken

  DOI：10.1021/ja402569j

  日期：2013.6.26

  We report a strategy for the conversion of aldehydes to enantiomerically enriched alpha-amino boronates through the intermediacy of in situ-generated silylimines. This transformation is brought about by Pt-catalyzed asymmetric addition of B-2(pin)(2) across the imine double bond. An attractive feature of the intermediate diboration adduct is that it can be acylated directly and provides convenient access to important N-acyl alpha-amino boronic ester derivatives.
• Evidence for the importance of π-π-attractive interactions in Enantioselective Diels-Alder reactions chiral catalysts of type (RO)2TiCl2
  作者：E.J. Corey、Yasushi Matsumura

  DOI：10.1016/0040-4039(91)80149-z

  日期：1991.10

  with Ti(Oi-Pr)4 followed by SiCl4 results in formation of the Ti (IV) complex 5 which is an exceptionally effective catalyst for enantioselective Diels-Alder reactions. The origin of the high enantioselectivities which have been observed (>95 : 5) probably lies in attractive π-π interaction between an aromatic group and the dienophile as indicated in formula 7.

  二醇4与Ti（Oi-Pr）4继之以SiCl 4的反应导致形成Ti（IV）配合物5，该配合物是对映选择性Diels-Alder反应非常有效的催化剂。如式7所示，已观察到的高对映选择性（> 95：5）的起源可能在于芳族基团与亲二烯体之间有吸引力的π-π相互作用。