Methyl (S)-α-hydroxycyclohexaneacetate | 121099-13-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Methyl (S)-α-hydroxycyclohexaneacetate
• 英文别名: Methyl (S)-2-hydroxy-2-cyclohexylacetate；(S)-methyl hexahydromandelate；methyl (2S)-2-cyclohexyl-2-hydroxyacetate
• CAS: 121099-13-6
• 化学式: C₉H₁₆O₃
• 分子量: 172.224
• InChiKey: LJJCBCPCMQLBCG-QMMMGPOBSA-N

物化性质

• 沸点：
  253.8±13.0 °C(Predicted)
• 密度：
  1.079±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  2-碘苯-1,3-二醇 、 Methyl (S)-α-hydroxycyclohexaneacetate 在 偶氮二甲酸二异丙酯 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  一种用于高对映选择性抗马尔可夫尼科夫氢胺化的手性 C2 对称芳硫醇催化剂

  摘要：

  手性氢供体催化剂的开发是通过对映选择性氢原子转移（HAT）过程扩展和创新不对称有机催化反应的基础。在此，开发了一种前所未有的手性C 2 -对称芳硫醇催化剂，其衍生自容易获得的对映体乳酸酯。利用这些催化剂，建立了不对称反马尔可夫尼科夫烯烃氢胺化环化反应，提供了多种具有中等到高对映选择性的药学上有趣的3-取代哌啶。设计的对照实验和理论计算的结果合理化了立体控制的起源，并揭示了手性硫醇部分对对映选择性的空间效应。我们相信这些催化剂的简便合成、灵活可调性和有效的对映选择性控制能力将为多功能手性 HAT 催化剂和相关不对称反应的开发提供线索。

  DOI：

  10.1021/jacs.4c04596
• 作为产物：
  描述：

  1,1,1-三氯(环己基)乙烷-2-酮 在 oxazaborolidine catalyst 2 sodium hydroxide 、 ammonium cerium(IV) nitrate 、 苄基三乙基氯化铵 、 儿萘酚硼烷 作用下， 以 乙二醇二甲醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 67.0h， 生成 Methyl (S)-α-hydroxycyclohexaneacetate
  参考文献：
  名称：

  手性α-芳氧基-和α-羟基酸对映选择性合成的新方法

  摘要：

  通过催化对映选择性还原三氯甲基酮容易获得的手性三氯甲基甲醇3通过构型转化转化为手性α-芳氧基和α-羟基羧酸衍生物。

  DOI：

  10.1016/s0040-4039(00)92655-8

文献信息

• Cationic BINAP-Ru(II) Halide Complexes: Highly Efficient Catalysts for Stereoselective Asymmetric Hydrogenation of .alpha.- and .beta.-Functionalized Ketones
  作者：Kazushi Mashima、Koh-hei Kusano、Naomasa Sato、Yoh-ichi Matsumura、Kyoko Nozaki、Hidenori Kumobayashi、Noboru Sayo、Yoji Hori、Takero Ishizaki

  DOI：10.1021/jo00090a026

  日期：1994.6

  Cationic ruthenium-BINAP complexes 5, 7, and 10 of the formula [RuX((S)-BINAP) (arene)]Y, where X = Cl, Br, I; Y = Cl, Br, I, BF4, B(C6H5)(4); arene = benzene, p-cymene, ethyl benzoate, and their enantiomers have been prepared by the reaction of arene-ruthenium halide complexes 4, 6, and 9 with (S)-BINAP or (R)-BINAP. Structures of the complexes were established by spectroscopy, conductivity, and a single-crystal X-ray analysis (5d: orthorhombic, P2(1)2(1)2; a 20.141(2) Angstrom, b = 18.504(1) Angstrom, c 12.241(1) Angstrom V = 4562.0(7) Angstrom(3), Z = 4, R = 0.078 for unique 4177 reflections). BINAP derivatives with various substituents at the para and meta positions of four phenyl rings on phosphorus atoms and their cationic Ru(II) complexes have also been synthesized. These BINAP-Ru(II) complexes have been used as catalysts for the asymmetric hydrogenation of various unsaturated organic compounds such as alpha- and beta-keto esters, allylic alcohols, and alpha,beta-unsaturated carboxylic acids in excellent diastereo- and/or enantioselectivities. Catalytic activities and stereoselectivities depend highly on reaction conditions such as solvent, temperature, and additives. Variation of halogen ligands bound to ruthenium atom and substituents on four phenyl rings of BINAP also have exerted remarkable effects on the efficiency of the catalysis. Asymmetric hydrogenation of methyl (+/-)-2-(benzamidomethyl)-3-oxobutanoate catalyzed by the species derived from 9c and 3,5((t)Bu)(2)-BINAP afforded the corresponding syn-(2S,3R)-17 in 98% de and 99% ee.
• Cesium fluoride-promoted esterification of carboxylic acids. A practical alternative to the diazomethane method and direct conversion of organotin carboxylates
  作者：Tsuneo Sato、Junzo Otera、Hitosi Nozaki

  DOI：10.1021/jo00033a048

  日期：1992.3
• Gerlach, Uwe; Haubenreich, Thomas; Huenig, Siegfried, Chemische Berichte, 1994, vol. 127, # 10, p. 1969 - 1980
  作者：Gerlach, Uwe、Haubenreich, Thomas、Huenig, Siegfried

  DOI：——

  日期：——
• Stereoselective reduction of C=X by a chiral 1,4-dihydropyridine (NADH-MIMIC) in a self-immolative process
  作者：A.I. Meyers、Jack D. Brown

  DOI：10.1016/s0040-4039(00)80827-8

  日期：1988.1
• Intermolecular and Intramolecular Reactions of Resolved 2-Alkoxytetrahydrofuran-3-yl and 2-Alkoxytetrahydropyran-3-yl Radicals
  作者：Kalpana S Nimkar、Eugene A Mash

  DOI：10.1016/s0040-4020(00)00547-0

  日期：2000.8

  Diastereomeric trans-2-alkoxy-3-phenylselenenyltetrahydrofuranyl acetals and trans-2-alkoxy-3-phenyl-selenenyltetrahydropyranyl acetals were prepared from dihydrofuran, dihydropyran, phenylselenenyl bromide, and the alcohols (S)-methyl lactate, (S)-methyl hexahydromandelate, and (R)-pantolactone. The diastereomers were chromatographically separated and were subjected to intermolecular alkylation via generation and trapping of free radicals. Observed diastereoselectivity was higher for 2-alkoxytetrahydrofuran-3-yl radicals than for 2-alkoxytetrahydropyran-3-yl radicals, and highest for acetals involving (R)-pantolactone. Alcohol exchanges at the anomeric carbon were highly stereocontrolled, and permitted introduction of alkenes for intramolecular trapping of free radical intermediates. (C) 2000 Elsevier Science Ltd. All rights reserved.