(1S,2R)-bis(2-hydroxybornane-10-yl)disulfide | 116195-09-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1S,2R)-bis(2-hydroxybornane-10-yl)disulfide
• 英文别名: bis-{(1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]hept-1-ylmethyl}disulfide；Diisobornyl 10-disulfide；(S,S)-diisobornyl-10-disulfide；1,1'-[Disulfanediylbis(methanediyl)]bis-[(1s,2r,4r)-7,7-dimethylbicyclo[2.2.1]heptan-2-ol]；(1S,2R,4R)-1-[[[(1S,2R,4R)-2-hydroxy-7,7-dimethyl-1-bicyclo[2.2.1]heptanyl]methyldisulfanyl]methyl]-7,7-dimethylbicyclo[2.2.1]heptan-2-ol
• CAS: 116195-09-6
• 化学式: C₂₀H₃₄O₂S₂
• 分子量: 370.621
• InChiKey: KBNUTAQBWKGTPY-LYYPEUCTSA-N

物化性质

• 熔点：
  159-160 °C(Solvent: Hexane)
• 沸点：
  478.7±10.0 °C(Predicted)
• 密度：
  1.186±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  91.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2R)-bis(2-hydroxybornane-10-yl)disulfide 在 4-二甲氨基吡啶 、 2-氮杂金刚烷-N-氧自由基 、 copper(l) chloride 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以92%的产率得到(S,S)-dicamphoryl-10-disulfide
  参考文献：
  名称：

  2-Azaadamantane N-氧基（AZADO）/ Cu催化可实现含电子丰富的二价硫官能团的醇的化学选择性好氧氧化

  摘要：

  在现代有机化学中，有时将含有富电子功能的硫官能团（例如1,3-二硫醚和硫化物）的醇化学选择性氧化成其相应的具有硫基的羰基化合物，这可能是一项艰巨的任务。报道了这种转化的可靠方法，其特征在于使用环境空气作为末端氧化剂的氮杂金刚烷型硝基氧基自由基/铜催化。通过与各种常规醇氧化方法进行比较，证明了所开发方法的优越性。

  DOI：

  10.1021/acs.orglett.8b02528
• 作为产物：
  描述：

  dimethyl (1S,2S,3R,4R)-2-((R)-(((1S,2R,4R)-2-hydroxy-7,7-dimethylbicyclo[2.2.1]heptan-1-yl)methyl)sulfinyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate 在 samarium diiodide 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲苯 、 叔丁醇 为溶剂， 反应 0.17h， 生成 (1S,2R)-bis(2-hydroxybornane-10-yl)disulfide
  参考文献：
  名称：

  Arai, Yoshitsugu; Matsui, Makoto; Koizumi, Toru, Journal of the Chemical Society. Perkin transactions I, 1990, # 4, p. 1233 - 1234

  摘要：

  DOI：

文献信息

• Unexpected conversion of vinyl sulfoxides into carbonyl compounds by means of iodotrimethylsilane
  作者：Maria C Aversa、Anna Barattucci、Paola Bonaccorsi、Giuseppe Bruno、Placido Giannetto、Manuela Policicchio

  DOI：10.1016/s0040-4039(00)00612-2

  日期：2000.6

  The unexpected and previously unknown TMSI-promoted conversion of α,β-unsaturated sulfoxides into carbonyl compounds and disulfides is described. It occurs in good yields under mild conditions. The examples provided support the generality and efficiency of this procedure which acts as a good method for removing the sulfinyl group with the advantage of transforming the vinyl sulfoxides into carbonyl

  描述了出乎意料且以前未知的TMSI促进的α，β-不饱和亚砜转化为羰基化合物和二硫化物。在温和条件下产量高。所提供的实施例支持了该方法的一般性和效率，该方法是除去亚磺酰基的良好方法，具有将乙烯基亚砜转化为羰基化合物的优点。
• A new resolution procedure for the preparation of both (R)-(+)- and (S)-(-)-4-tert-butoxycyclopent-2-enone from racemic 4-tert-butoxycyclopent-2-enone and conversion of (R)-(+)-4-tert-butoxycyclopent-2-enone into (R)-(+)-4-acetoxycyclopent-2-enone. A new method for the determination of the enantiomeric purities of the resolved enones
  作者：Bart M. Eschler、Richard K. Haynes、Michael D. Ironside、Steve Kremmydas、Damon D. Ridley、Trevor W. Hambley

  DOI：10.1021/jo00015a035

  日期：1991.7

  (1S)-(-)-10-Mercaptoisoborneol undergoes conjugate addition to (+/-)-4-tert-butoxycyclopent-2-enone in methanol containing N,N,N',N'-tetramethylethylenediamine to give a 1:1 mixture of diastereomers of 3-tert-butoxy-4-[[(exo-2'-hydroxy-7',7'-dimethylbicyclo[2.2.1]heptanyl)methyl]thio]cyclopentanone in 93-95% yield. The mixture is converted by m-chloroperbenzoic acid into the corresponding sulfoxide mixture. The (3R,4R,R(S))-sulfoxide isomer, whose absolute configuration has been determined by X-ray crystallography, crystallizes cleanly from this mixture in an enantiomeric yield of 76% from the corresponding sulfide. It is decomposed on silica gel to generate (R)-(+)-4-tert-butoxycyclopent-2-enone, with an enantiomeric purity of greater-than-or-equal-to 99.9% in 92% yield from the sulfoxide, and 10-thiodiisobornyl 10'-sulfoxide. Similarly, the (S)-(-)-enone is prepared from (1R)-(+)-10-mercaptoisoborneol. The (+/-)- and the (R)-(+)-enone, respectively, are converted by a catalytic amount of FeCl3 in acetic anhydride into (+/-)- and (R)-(+)-4-acetoxycyclopent-2-enone (with an enantiomeric purity of greater-than-or-equal-to 99.9%) in 80% yield. The enantiomeric purity of the products was assessed through their treatment with (-)-10-mercaptoisoborneol and analysis of the adducts by HPLC and 400-MHz H-1 NMR spectroscopy.

  (1S)-(-)-10-巯基异冰片在含有N,N,N',N'-四甲基乙二胺的甲醇中与(+/-)-4-叔丁氧基环戊-2-烯酮发生共轭加成，得到3-叔丁氧基-4-[[(exo-2'-羟基-7',7'-二甲基双环[2.2.1]庚烷基)甲基]硫代]环戊酮的两种异构体(1:1比例)的混合物，收率93-95%。该混合物在过氯苯甲酸作用下转化为相应的硫氧化物混合物。通过X射线晶体学确定了绝对构型的(3R,4R,R(S))-硫氧化物异构体从该混合物中以76%的手性收率析出。在二氧化硅胶上分解此硫氧化物可得到(R)-(+)-4-叔丁氧基环戊-2-烯酮(手性纯度≥99.9%)，以及10-硫二异冰片-10'-硫氧化物，产率为92%。同样，(S)-(-)-烯酮可由(1R)-(+)-10-巯基异冰片制得。在醋酐中添加催化量的FeCl3，(±)-和(R)-(+)-烯酮分别转化为(+/-)-和(R)-(+)-4-乙酰氧基环戊-2-烯酮(手性纯度≥99.9%)，收率为80%。产物的手性纯度通过与(-)-10-巯基异冰片的处理及其加成物的HPLC和400 MHz H-1 NMR光谱分析确定。
• Synthesis of chiral vinylic sulfoxides by Pd-catalyzed asymmetric sulfinylzincation
  作者：Naoyoshi Maezaki、Suguru Yagi、Shizuka Ohsawa、Hirofumi Ohishi、Tetsuaki Tanaka

  DOI：10.1016/j.tet.2003.10.037

  日期：2003.12

  Novel asymmetric sulfinylzincation of alkynoates has been accomplished via a Pd-catalyzed sulfinylzincation using 1-alkynyl sulfoxides bearing chiral auxiliaries as a sulfinylating reagent. The reaction proceeded in a highly syn-selective fashion, giving the (E)-beta-sulfinyl alpha,beta-unsaturated ester exclusively. Among the chiral sulfinylating reagents tested, an isoborneol-type compound (Rs)-4 showed the best results in terms of both yield and diastereoselectivity. As a result of optimization of the reaction, the selectivity was improved up to 92:8 dr, and stereochemistry of the newly formed sulfur stereogenic center was revealed as (Ss)-configuration. (C) 2003 Elsevier Ltd. All rights reserved.
• Arai, Yoshitsugu; Matsui, Makoto; Fujii, Akihito, Journal of the Chemical Society. Perkin transactions I, 1994, # 1, p. 25 - 40
  作者：Arai, Yoshitsugu、Matsui, Makoto、Fujii, Akihito、Kontani, Tohru、Ohno, Toshiyuki、et al.

  DOI：——

  日期：——
• Arai, Yoshitsugu; Hayashi, Kazuya; Matsui, Makoto, Journal of the Chemical Society. Perkin transactions I, 1991, # 7, p. 1709 - 1716
  作者：Arai, Yoshitsugu、Hayashi, Kazuya、Matsui, Makoto、Koizumi, Toru、Shiro, Motoo、Kuriyama, Kaoru

  DOI：——

  日期：——