(S,S)-(+)-1-苯基环己烷-顺-1,2-二醇 | 34281-90-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (S,S)-(+)-1-苯基环己烷-顺-1,2-二醇
• 中文别名: (S,s)-(+)-1-苯基环己烷-顺式-1,2-二醇；(S,S)-(+)-1-苯基环己烷-顺式-1,2-二醇
• 英文名称: (1S,2S)-1-phenyl-1,2-cyclohexanediol
• 英文别名: 1-phenylcyclohexane-1,2-diol；(1S,2S)-1-Phenylcyclohexane-1,2-diol
• CAS: 34281-90-8
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: QHNHEYDAIICUDL-RYUDHWBXSA-N

物化性质

• 熔点：
  121-123 °C(lit.)
• 沸点：
  322.7±42.0 °C(Predicted)
• 密度：
  1.179±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

安全信息

• WGK Germany：
  3
• 海关编码：
  2906299090

反应信息

• 作为反应物：
  描述：

  (S,S)-(+)-1-苯基环己烷-顺-1,2-二醇 在 lithium aluminium tetrahydride 、 sodium azide 、 高氯酸 、 乙酸酐 、 sodium hydride 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 128.5h， 生成
  参考文献：
  名称：

  Homochiral ligands derived from cis-1-phenylcyclohexane-1,2-diol and cis-2-azido-2-phenylcyclohexanol

  摘要：

  Homochiral ligands (R,R)-2, (R,R)-3a, (R,R)-3b, (S,S)-4a, and (S,S)-4b were prepared from cis-1-phenylcyclohexane-1,2-diol or cis-2-azido-2-phenylcyclohexanol and were tested as ligands for the nucleophilic addition of alkyllithiums to benzaldehyde 4-anisidineimine. While moderate enantioselectivities (up to 43% e.e.) were observed with (R,R)-3b and (S,S)-4a, (R,R)-2 and (R,R)-3a did not show enantioselectivities. Homochiral secondary amines (S,S)-6a and (S,S)-6b were also prepared from cis-2-azido-2-phenylcyclohexanol. Moderate enantioselectivities (up to 50%) were observed-when they were used as chiral lithium amide base precursors for the deprotonation of 4-t-butylcyclohexanone. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00552-1
• 作为产物：
  描述：

  cis-acetic acid 2-hydroxy-2-phenyl-cyclohexyl ester 在 Porcine Pancreas Lipase 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 114.0h， 生成 (S,S)-(+)-1-苯基环己烷-顺-1,2-二醇
  参考文献：
  名称：

  Naemura, Koichiro; Miyabe, Hajime; Shingai, Yasuhiro, Journal of the Chemical Society. Perkin transactions I, 1991, # 4, p. 957 - 959

  摘要：

  DOI：

文献信息

• A mechanistically designed mono-cinchona alkaloid is an excellent catalyst for the enantioselective dihydroxylation of olefins
  作者：E.J. Corey、Mark C. Noe、Michael J. Grogan

  DOI：10.1016/s0040-4039(00)78237-2

  日期：1994.8

  advanced regarding the origin of enantioselectivity in the OsO4-promoted dihydroxylation of olefins catalyzed by bis-cinchona alkaloid derivatives such as 1, specifically strong evidence for reaction via transition state assembly 2, the mono-quinidine derivative 3 was selected as a promising catalytic ligand. The experimental observation of high enantioselectivity promoted by 3 provides additional

  根据最近提出的关于OsO 4促进的由双金鸡纳生物碱衍生物（例如1）催化的烯烃的二羟基化中对映选择性的起源的想法，特别是有强有力的证据证明通过过渡态组装体2可以进行反应，单奎尼丁衍生物3是被选为有前途的催化配体。由3促进的高对映选择性的实验观察提供了有利于过渡态2的其他证据。
• Markedly enhanced recyclability of osmium catalyst in asymmetric dihydroxylation reactions by using macroporous resins bearing both residual vinyl groups and quaternary ammonium moieties
  作者：Kwang Jin Kim、Han Young Choi、Soon Ho Hwang、Yil Sung Park、Eun Kyung Kwueon、Doo Seong Choi、Choong Eui Song

  DOI：10.1039/b504223b

  日期：——

  Markedly enhanced recyclability of osmium catalyst in asymmetric dihydroxylation has been achieved by using osmylated macroporous resins bearing both residual vinyl groups and quaternary ammonium moiety.

  通过使用同时含有残留乙烯基团和季铵基团的锇配合大孔树脂，显著提高了不对称二羟基化反应中锇催化剂的可回收性。
• Syn-Dihydroxylation of Alkenes Using a Sterically Demanding Cyclic Diacyl Peroxide
  作者：Afsaneh Pilevar、Abolfazl Hosseini、Jonathan Becker、Peter R. Schreiner

  DOI：10.1021/acs.joc.9b01748

  日期：2019.10.4

  alkenes is a highly valuable reaction in organic synthesis. Cyclic acyl peroxides (CAPs) have emerged recently as promising candidates to replace the commonly employed toxic metals for this purpose. Here, we demonstrate that the structurally demanding cyclic peroxide spiro[bicyclo[2.2.1]heptane-2,4'-[1,2]dioxolane]-3',5'-dione (P4) can be effectively used for the syn-dihydroxylation of alkenes. Reagent

  烯烃的顺二羟基化是有机合成中非常有价值的反应。环状酰基过氧化物（CAPs）最近作为有前途的候选物出现，以取代通常用于此目的的有毒金属。在这里，我们证明了结构上苛刻的环状过氧化物螺[双环[2.2.1]庚烷-2,4'-[1,2]二氧戊环] -3'，5'-二酮（P4）可以有效地用于合成烯烃的-二羟基化。与其他CAP和二醇与烯丙醇产品相互竞争的CAP相比，试剂P4还显示出对带有β-氢的烯烃进行二羟基化的选择性提高。此外，对映纯P4（标记为P4'）的使用证明了P4'对于烯烃的无金属不对称顺二羟基化反应的潜力。
• A New Practical Method for the Osmium-Catalyzed Dihydroxylation of Olefins­ using Bleach as the Terminal Oxidant
  作者：Matthias Beller、Gerald M. Mehltretter、Santosh Bhor、Markus Klawonn、Christian Döbler、Uta Sundermeier、Markus Eckert、Hans-Christian Militzer

  DOI：10.1055/s-2003-36826

  日期：——

  A general procedure for the osmium-catalyzed dihydroxylation of various olefins using bleach as oxidant is reported for the first time. Aromatic and aliphatic olefins yield the corresponding cis-1,2-diols in the presence of dihydroquinine or dihydroquinidine derivatives (Sharpless ligands) with good to excellent chemo- and enantioselectivities under optimized pH conditions. In the presence of a small

  首次报道了使用漂白剂作为氧化剂对各种烯烃进行锇催化二羟基化的一般程序。芳香族和脂肪族烯烃在二氢奎宁或二氢奎尼丁衍生物（Sharpless 配体）存在下产生相应的 cis-1,2-二醇，在优化的 pH 条件下具有良好至优异的化学和对映选择性。在少量过量的漂白剂作为再氧化剂的情况下，即使在 0°C 也会发生快速二羟基化。在最佳反应条件下，可以将末端脂肪族和芳香族烯烃以及内烯烃二羟基化。氧化剂的低价和漂白剂的简单处理使这种二羟基化变体对进一步的应用具有吸引力。
• Catalytic Asymmetric Dihydroxylation of C,C Double Bonds with Osmium Tetroxide Using Selenoxides as Co-oxidants
  作者：Alain Krief、Catherine Castillo-Colaux

  DOI：10.1055/s-2001-12437

  日期：——

  Asymmetric dihydroxylation of olefins has been achieved in good yields and ee's using potassium osmate dihydrate (K2OsO2(OH)4, the pre-oxidant), (DHQD)2PHAL (the chiral ligand), potassium carbonate (the base) and selenoxides (the co-oxidants). Both the yield and the ee proved to be pH dependent, the highest yield and ee being found at almost the same pH values. The rate of the reaction was found to be highly dependent upon the structure of the selenoxide used. Some representative examples involving aminoxides are presented for comparison.

  不对称二羟基化反应已成功实现，使用了二水合钾钼酸盐（K2OsO2(OH)4，氧化剂）、（DHQD）2PHAL（手性配体）、碳酸钾（碱）和硒氧化物（共同氧化剂），yield 和 ee 均表现出 pH 依赖性，最高的 yield 和 ee 出现在几乎相同的 pH 值下。此外，反应速率还发现高度依赖于所用硒氧化物的结构。文中还提供了一些涉及氨氧化物的代表性例子以作比较。