(1S,2R,3S)-2-formyl-6,6-dimethyl-3-acetylthiobicyclo[3.1.1]heptane | 444308-37-6

• 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,3S)-2-formyl-6,6-dimethyl-3-acetylthiobicyclo[3.1.1]heptane
• 英文别名: S-(6,6-dimethyl-2-formylnorpinan-3-yl) thioacetate；S-(1s,2r,3s,5r)-2-formyl-6,6-dimethylnorpinan-3-yl thioacetate；S-[(1S,2R,3S,5R)-2-formyl-6,6-dimethyl-3-bicyclo[3.1.1]heptanyl] ethanethioate
• CAS: 444308-37-6
• 化学式: C₁₂H₁₈O₂S
• 分子量: 226.34
• InChiKey: VVFCMCTWOUXUEM-RCWTZXSCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  59.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2R,3S)-2-formyl-6,6-dimethyl-3-acetylthiobicyclo[3.1.1]heptane 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 10-hydroxyisopinocampheylthiol
  参考文献：
  名称：

  Synthesis of acyldodecaheterocycles derived from (1R)-(–)-myrtenal and evaluation as chiral auxiliaries

  摘要：

  New (1R)-(-)-myrtenal-derived macrocycles 5a and 5b were efficiently used as chiral auxiliaries in the diastereoselective nucleophilic addition of several nucleophiles (RMgX, RLi, LiAlH4, and NaBH4). We observed that the diastereoselectivity depended on the nucleophile, with the stereoselectivity order being RMgX (>99:1 dr) > RLi (7:3 dr) > AlLiH4 >= NaBH4 (6:4 dr). The absolute configuration of the resulting carbinols was established by X-ray diffraction of adducts 9a and 9b, and through chemical correlation of carbinols 9b and 9c with diols of known absolute configuration. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.10.013
• 作为产物：
  描述：

  桃金娘烯醛 、 硫代乙酸 在 吡啶 作用下， 生成 (1S,2R,3S)-2-formyl-6,6-dimethyl-3-acetylthiobicyclo[3.1.1]heptane
  参考文献：
  名称：

  Synthesis of acyldodecaheterocycles derived from (1R)-(–)-myrtenal and evaluation as chiral auxiliaries

  摘要：

  New (1R)-(-)-myrtenal-derived macrocycles 5a and 5b were efficiently used as chiral auxiliaries in the diastereoselective nucleophilic addition of several nucleophiles (RMgX, RLi, LiAlH4, and NaBH4). We observed that the diastereoselectivity depended on the nucleophile, with the stereoselectivity order being RMgX (>99:1 dr) > RLi (7:3 dr) > AlLiH4 >= NaBH4 (6:4 dr). The absolute configuration of the resulting carbinols was established by X-ray diffraction of adducts 9a and 9b, and through chemical correlation of carbinols 9b and 9c with diols of known absolute configuration. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.10.013

文献信息

• Synthesis of New Sulfonic Acid Derivatives by the Reaction of S-(1S,2R,3S,5R)-2-Formyl-6,6-dimethylnorpinan-3-yl Thioacetate with Chlorine Dioxide
  作者：S. N. Subbotina、O. N. Grebyonkina、P. V. Gribkov、D. P. Gerasimova、O. A. Lodochnikova、I. R. Gilfanov、L. E. Nikitina、O. M. Lezina、S. A. Rubtsova

  DOI：10.1134/s1070428024040079

  日期：2024.4

  Abstract New polyfunctional compounds of the pinane series, 2-carboxy-3-thioacetate, 2-carboxy-3-sulfonyl chloride, and 2-carboxy-3-sulfonic acid that are promising intermediate products in organic synthesis, were synthesized for the first time by the reaction of S-(1S,2R,3S,5R)-(6,6-dimethyl-2-formylnorpinan-3-yl) thio­acetate with chlorine dioxide. The major reaction pathway in nonpolar solvents

  抽象的 首次合成了蒎烷系列的新型多官能化合物2-羧基-3-硫代乙酸酯、2-羧基-3-磺酰氯和2-羧基-3-磺酸，这些化合物是有前途的有机合成中间体产品。 S-(1S,2R,3S,5R)-(6,6-二甲基-2-甲酰基去蒎南-3-基)硫代乙酸酯与二氧化氯反应。非极性溶剂中的主要反应途径涉及醛基氧化成羧基，而在高极性溶剂中则发生硫原子的氧化，然后脱乙酰化。揭示了 VO(acac) 2 作为催化剂对弱极性乙醚反应化学选择性的影响。
• Highly diastereoselective nucleophilic additions using a novel myrtenal-derived oxathiane as a chiral auxiliary
  作者：Federico Martı́nez-Ramos、Marı́a Elena Vargas-Dı́az、Luis Chacón-Garcı́a、Joaquı́n Tamariz、Pedro Joseph-Nathan、L.Gerardo Zepeda

  DOI：10.1016/s0957-4166(01)00545-6

  日期：2001.12

  The synthesis of novel oxathiane 3 and its acetyl derivative 12, from commercially available (-)myrtenal 4, is described. The addition of several nucleophilic reagents to 12 furnished the corresponding tertiary carbinols in highly diastereomeric excess. The hydrolysis of 11a, b yielded the expected alpha-hydroxycarbonyl compounds in excellent enantiomeric excess. (C) 2002 Elsevier Science Ltd. All rights reserved.
• New 1,3-Oxathianes Derived from Myrtenal:  Synthesis and Reactivity
  作者：Arlette Solladié-Cavallo、Milan Balaz、Marta Salisova、Richard Welter

  DOI：10.1021/jo034404w

  日期：2003.8.1

  2-Methyl- and 2-phenyl-substituted oxathianes derived from Myrtenal have been synthesized in satisfying yields. Lithiation of 2-methyl-substituted oxathiane could not be done, but lithiation of 2-phenyl-substituted and non-substituted oxathianes could be performed with s-BuLi. Quenching with D2O, TMSCl, and/or a carbonyl compound always provides the equatorial product in consistency with a prefered equatorial orientation of the lithium in the lithiated derivatives. A model is proposed to rationalize the diastereoselectivities observed at C5' during reaction of aldehydes with lithiated non-substituted oxathiane. The model is based on the hypothesis that the lithium, being-linked simultaneously to the carbon and the oxygen, is shifted toward the oxygen side, making the steric hindrance of this side more effective. Dimeric side products were observed during formation of these oxathianes (condensation of various aldehydes with the corresponding hydroxythiol), which had not been reported for other oxathianes (derived from pulegone and/or camphorsulfonic,acid).