(1R,2S,3R)-3-mercapto-1,7,7-trimethylbicyclo{2.2.1}heptan-2-ol | 132609-85-9

• 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: (1R,2S,3R)-3-mercapto-1,7,7-trimethylbicyclo{2.2.1}heptan-2-ol
• 英文别名: (1R,2S,3R)-3-mercaptocamphan-2-ol；3-mercaptoisoborneol；(1R,2S,3R,4S)-1,7,7-trimethyl-3-sulfanylbicyclo[2.2.1]heptan-2-ol
• CAS: 132609-85-9
• 化学式: C₁₀H₁₈OS
• 分子量: 186.318
• InChiKey: LOMPQMWIMBEFQB-DQUBFYRCSA-N

物化性质

• 沸点：
  255.7±23.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  21.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2S,3R)-3-mercapto-1,7,7-trimethylbicyclo{2.2.1}heptan-2-ol 在 N-氯代丁二酰亚胺 、 氨 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以58%的产率得到(1R,2S,3R,4S)-3-aminosulfanyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol
  参考文献：
  名称：

  Application of New Camphor-Derived Mercapto Chiral Auxiliaries to the Synthesis of Optically Active Primary Amines

  摘要：

  A series of enantiomerically pure sulfinimines carrying new camphor-based mercapto chiral auxiliaries are subjected to asymmetric alkylation. Such reaction offers an excellent route to the preparation of optically active primary amines. Also reported here is an unprecedented Grignard addition of a chiral sulfenimine leading to a single enantiomer of the corresponding sulfenamide and thence produced enantiopure amine after acidic aqueous workup. The chiral auxiliary can be recovered in high yield.

  DOI：

  10.1021/jo00083a037
• 作为产物：
  描述：

  (1R,2S,3R,4S)-3-[(E)-benzylideneamino]sulfanyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol 在 盐酸 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 生成 (1R,2S,3R)-3-mercapto-1,7,7-trimethylbicyclo{2.2.1}heptan-2-ol
  参考文献：
  名称：

  Application of New Camphor-Derived Mercapto Chiral Auxiliaries to the Synthesis of Optically Active Primary Amines

  摘要：

  A series of enantiomerically pure sulfinimines carrying new camphor-based mercapto chiral auxiliaries are subjected to asymmetric alkylation. Such reaction offers an excellent route to the preparation of optically active primary amines. Also reported here is an unprecedented Grignard addition of a chiral sulfenimine leading to a single enantiomer of the corresponding sulfenamide and thence produced enantiopure amine after acidic aqueous workup. The chiral auxiliary can be recovered in high yield.

  DOI：

  10.1021/jo00083a037

文献信息

• The study of Lewis acid effect on asymmetric Diels-Alder reactions of new 2-sulfinylbutadienes derived from (1R, 2S, 3R)-3-mercaptocamphan-2-ol
  作者：Teng-Kuei Yang、Han-Yang Chu、Dong-Sheng Lee、Yao-Zhong Jiang、Ta-Shue Chou

  DOI：10.1016/0040-4039(96)00897-0

  日期：1996.6

  The Diels-Alder reactions of N-phenylmaleimide and new chiral 2-sulfinylbutadienes, which were prepared from , produced cycloadducts up to 99% d.e. in the presence of LiClO4 at ambient temperature. On the other hand, we found the facial selectivity of the cycloaddtion changed greatly among various Lewis acids.

  在环境温度下，在LiClO 4存在下，由N-苯基马来酰亚胺和新的手性2-亚磺酰基丁二烯制备的狄尔斯-阿尔德反应可生成高达99％de的环加合物。另一方面，我们发现在各种路易斯酸之间，环加成反应的面部选择性发生了很大变化。
• Synthesis, characterization, and structures of Group IV metallocene complexes of heterodifunctional ligands containing oxygen and sulfur donor atoms
  作者：Han Mou Gau、Chien An Chen、Shiow Jiuan Chang、Wei En Shih、Teng Kuei Yang、Ting Ting Jong、Mei Yueh Chien

  DOI：10.1021/om00028a054

  日期：1993.4

  The interaction of the chiral difunctional ligand (1R,2S,3R)-3-mercapto-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol (1) with group IV metallocene complexes affords the product Cp2M(OC10H16S) (Cp = cyclopentadienyl; M = Ti (2) or Zr (3); OC10H16S = (1R,2S,3R)-3-thio-1,7,7-trimethylbicyclo[2.2.1]heptan-2-olato). In CDCl3 solution, complex 3 exists as a mixture of a monomeric species and an associated dimeric species. Complex 3 readily hydrolyzes to give an air-stable complex, [CP2Zr(mu-O) (mu-OC10H16S)ZrCp2)] (4). The complex 4 crystallizes in the orthorhombic space group P2(1)2(1)2, with cell parameters a = 10.061 (2) angstrom, b = 15.476 (4) angstrom, c = 17.741 (3) angstrom, v = 2762.4 (10) angstrom3 R = 0.044, and R(W) = 0.052. The complex 4 is an oxo-bridged zirconocene dimer that is also bridged by a heterodifunctional ligand. The Zr-O-Zr angle is small at 139.9 (2)-degrees, and the Zr...Zr distance is 3.685 angstrom. Two zirconocene moieties are inequivalent due to the asymmetric difunctional ligand. The related complex [CP2Zr(mu-OCH2CH2S)]2 (5) was also prepared. Complex 5 crystallizes in the monoclinic space group P2(1)/c with cell parameters a = 16.730 (3) angstrom, b = 8.232 (2) angstrom, c = 17.570 (2) angstrom, beta = 111.21 (2)-degrees, V = 2255.9 (7) angstrom3, R = 0.034, and R(w) = 0.045. The complex 5 is a zirconocene dimer bridging through the oxygen atoms. The ZrOZrO framework is nearly planar with both sulfur atoms above the plane by approximately 0.45 angstrom, and the Zr...Zr distance at 3.719 angstrom is somewhat longer than that in complex 4.
• New Chiral Phosphinooxathiolane Ligands for Palladium-catalyzed Asymmetric Allylations
  作者：Hiroto Nakano、Yuko Okuyama、Ryo-suke Takahashi、Reiko Fujita

  DOI：10.3987/com-03-s61

  日期：——

  A new chiral phosphinooxathiolane ligands were synthesized and their abilities as chiral catalysts were examined in palladium-catalyzed allylic alkylation and amination.
• 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.
• A new and highly enantioselective synthetic route to P-chiral phosphines and diphosphines
  作者：E. J. Corey、Zhuoliang Chen、Gerald J. Tanoury

  DOI：10.1021/ja00076a072

  日期：1993.11