(4R,5R)-dimethyl 2,2-diethyl-1,3-dioxolane-4,5-dicarboxylate | 112193-28-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,5R)-dimethyl 2,2-diethyl-1,3-dioxolane-4,5-dicarboxylate
• 英文别名: dimethyl (2R,3R)-2,3-O-(3-pentylidene)tartrate；3-pentylidene ketal of (R,R)-(+)-dimethyl tartrate；dimethyl (4R,5R)-2,2-diethyl-1,3-dioxolane-4,5-dicarboxylate
• CAS: 112193-28-9
• 化学式: C₁₁H₁₈O₆
• 分子量: 246.26
• InChiKey: OMXPSRLKRYONFO-HTQZYQBOSA-N

物化性质

• 沸点：
  286.7±35.0 °C(Predicted)
• 密度：
  1.121±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (4R,5R)-dimethyl 2,2-diethyl-1,3-dioxolane-4,5-dicarboxylate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 4.0h， 以85%的产率得到(4S,5S)-2,2-diethyl-4,5-bis(hydroxymethyl)-1,3-dioxolane
  参考文献：
  名称：

  Synthesis of methyl (E)-2-[(3S,4S)-4-hydroxy-3-(pent-3-yloxy)-pyrrolidin-2-ylidene]propanoate and its unusual recyclization

  摘要：

  (2E,4S,5S)-5-羟基-6-甲酰氧基-2-甲基-4-(戊-3-氧基)己-2-烯酸甲酯由酒石酸合成。尝试通过与 NaN3 反应取代间氧基，直接生成 (E)-2-[(3S,4S)-4- 羟基-3-(戊-3-氧基)吡咯烷-2-亚基]丙酸甲酯。后者经 CF3COOH 和 NaOH 处理后得到 (2E)-2- 甲基-4-[(S)-环氧乙烷-2-基]-4-(戊-3-氧基)丁-2-烯酸甲酯。

  DOI：

  10.1007/s11172-013-0168-0
• 作为产物：
  描述：

  L-(+)-酒石酸二甲酯 、 3-戊酮 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 生成 (4R,5R)-dimethyl 2,2-diethyl-1,3-dioxolane-4,5-dicarboxylate
  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

• Investigation of the Effects of the Structure and Chelate Size of Bis-oxazoline Ligands in the Asymmetric Copper-Catalyzed Cyclopropanation of Olefins:  Design of a New Class of Ligands
  作者：Ashutosh V. Bedekar、Elise B. Koroleva、Pher G. Andersson

  DOI：10.1021/jo962021a

  日期：1997.4.1

  D-tartaric acid, two sets of ligands (6b-e and 7a,b) were synthesized and evaluated in the copper-catalyzed cyclopropanation of olefins. The comparison of benzyl and isopropyl derivatives of these ligands with previously reported five- and six-membered bis-oxazolines clearly indicates the beneficiary effect of the larger chelate size and the chiral tether of the tartrate-derived ligand. The effect of the different

  通过将两个恶唑啉环安装到光学活性的1,3-二氧戊环骨架上，合成了一组新颖的C（2）对称双恶唑啉配体。该设计允许控制反应位点周围的恶唑啉基R基团的取向和邻近度。由于1，3-二氧戊环环的扭曲，可以以可控制的方式使立体异构的恶唑啉基取代基朝向或远离络合金属。从L-氨基醇和L-或D-酒石酸开始，合成了两组配体（6b-e和7a，b），并在铜的烯烃环丙烷化中进行了评估。这些配体的苄基和异丙基衍生物与先前报道的五元和六元双恶唑啉的比较清楚地表明，较大的螯合物大小和酒石酸衍生的配体的手性束缚带的有益作用。还研究了不同的恶唑啉基基团以及不同的取代基对二氧戊环系链的影响。研究了重氮乙酸酯的烷基的影响，发现衍生自（-）-8-苯基薄荷醇的重氮乙酸酯优于（-）-薄荷基重氮乙酸酯。乙酸乙烯酯的环丙烷化反应是该反应的一种相对未开发的底物，提供了良好光学纯度的环丙醇衍生物。还研究了不同的恶唑啉基基团以及不同的取代基对二氧
• Highly isotactic optically active methacrylate polymers by free radical cyclopolymerization
  作者：Shiying Zheng、Dotsevi Y. Sogah

  DOI：10.1016/s0040-4020(97)00974-5

  日期：1997.11

  Isospecific free radical cyclopolymerization of tartrate-based monomers gives polymers with very high optical rotations. Circular dichroism and polarimetric measurements suggest the polymers are rigid and ordered. Their high resistance to solvolysis suggests potential applications in chiral chromatography.

  基于酒石酸酯的单体的异种自由基环聚合反应使聚合物具有非常高的旋光度。圆二色性和极化测量表明聚合物是刚性的和有序的。它们对溶剂分解的高抵抗力表明其在手性色谱法中的潜在应用。
• 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.
• Process for preparing optically active carbonyl compounds
  申请人：ZAMBON S.p.A.

  公开号：EP0217375B1

  公开（公告）日：1991-01-16
• 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.