(1R,3S,5R)-6,6-Dimethyl-3-(phenylthio)bicyclo<3.1.1>heptane-2-one | 128301-59-7

• 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,3S,5R)-6,6-Dimethyl-3-(phenylthio)bicyclo<3.1.1>heptane-2-one
• 英文别名: (1R,3S,5R)-6,6-dimethyl-3-(phenylthio)bicyclo<3.1.1>heptan-2-one；(1R,3S,5R)-6,6-Dimethyl-3-(phenylthio)bicyclo[3.1.1]heptane-2-one；(1R,3S,5R)-6,6-dimethyl-3-phenylsulfanylbicyclo[3.1.1]heptan-2-one
• CAS: 128301-59-7
• 化学式: C₁₅H₁₈OS
• 分子量: 246.373
• InChiKey: OFEHVIIUZPQSAW-WXHSDQCUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,3S,5R)-6,6-Dimethyl-3-(phenylthio)bicyclo<3.1.1>heptane-2-one 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 苯 为溶剂， 以63%的产率得到(1R,3R,5R)-6,6-Dimethyl-3-(phenylthio)bicyclo<3.1.1>heptane-2-one
  参考文献：
  名称：

  通过使用亚磺酰基化-脱氢亚磺酰基化方法，从Nopinone制备旋光性Apoverbenone和Verbenone。亚砜中硫原子上绝对构型的稳定性和反应性。

  摘要：

  旋光形式的Apoverbenone（4）和verbenone（5）作为对映选择性合成中的手性来源，可能是有用的化合物。以易于从（-）-β-pine烯，（+）-apoverbenone（4a）和（+）-verbenone（5a）购得的（+）-nopinone（1）开始，以合成上令人满意的总收率制备，通常使用亚磺酰化-脱氢亚磺酰化方法涉及烯酮官能团的构建。该方法学可适用于从（-）-去甲酮开始制备其对映体（-）-4b和（-）-5b。虽然亚砜10a，b和18a，b中的苯亚磺酰基的构型是通过（1）H NMR光谱和NOE相关性确定的，但通过在（1）H NMR光谱中比较它们的同系物，可以得出硫原子的绝对构型绝对配置明确的 即10a与13a，10b与13b，18a与19b和18b与19a。结果证明，在3-（苯基亚磺酰基）nopinones中，异构体的热力学稳定性取决于硫中心的绝对构型；即，反式异构体10a

  DOI：

  10.1021/jo9807316
• 作为产物：
  描述：

  beta-pinene 在 甲醇 、 臭氧 、 lithium diisopropyl amide 作用下， 反应 29.33h， 生成 (1R,3S,5R)-6,6-Dimethyl-3-(phenylthio)bicyclo<3.1.1>heptane-2-one
  参考文献：
  名称：

  The use of 4,4-disubstituted nopinones for natural-product synthesis. Synthesis of elemanoid sesquiterpenes

  摘要：

  A general and convenient synthetic route to 4,4-disubstituted nopinones 14 from (+)-nopinone (1) is developed and applied to the asymmetric synthesis of some representative elemanoid sesquiterpenes. Phenylsulfenylation of 1 provided sulfide 6 in high yield. A convenient transformation of 6 to 3-(phenylsulfonyl)-4,4-disubstituted-nopinones 13 was accomplished by (i) m-CPBA oxidation of a sulfide compound followed by the Pummerer rearrangement and (ii) the conjugate addition of carbon nucleophiles to the resulting enones, 6 --> 8 --> 9 and 9 --> 10,11 --> 13. Subsequent reductive desulfurization of the adducts 13 provided 14 in good overall yield from 1. Bicyclic ketones 14 are envisioned as promising intermediates for natural product synthesis. As examples, syntheses of two elemanoid sesquiterpenes, beta-elemenone (16) and eleman-8-beta,12-olide (17) in optically active form from (1R,4S,5S)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one (14a) were carried out.

  DOI：

  10.1021/jo00025a023

文献信息

• Kato, Michiharu; Vogler, Bernhard; Tooyama, Youichi, Chemistry Letters, 1990, p. 151 - 154
  作者：Kato, Michiharu、Vogler, Bernhard、Tooyama, Youichi、Yoshikoshi,Akira

  DOI：——

  日期：——
• KATO, MICHIHARU;VOGLER, BERNHARD;TOOYAMA, YOUICHI;YOSHIKOSHI, AKIRA, CHEM. LETT.,(1990) N, C. 151-154
  作者：KATO, MICHIHARU、VOGLER, BERNHARD、TOOYAMA, YOUICHI、YOSHIKOSHI, AKIRA

  DOI：——

  日期：——
• The use of 4,4-disubstituted nopinones for natural-product synthesis. Synthesis of elemanoid sesquiterpenes
  作者：Michiharu Kato、Masataka Watanabe、Bernhard Vogler、Bahlul Z. Awen、Yoshiaki Masuda、Youichi Tooyama、Akira Yoshikoshi

  DOI：10.1021/jo00025a023

  日期：1991.12

  A general and convenient synthetic route to 4,4-disubstituted nopinones 14 from (+)-nopinone (1) is developed and applied to the asymmetric synthesis of some representative elemanoid sesquiterpenes. Phenylsulfenylation of 1 provided sulfide 6 in high yield. A convenient transformation of 6 to 3-(phenylsulfonyl)-4,4-disubstituted-nopinones 13 was accomplished by (i) m-CPBA oxidation of a sulfide compound followed by the Pummerer rearrangement and (ii) the conjugate addition of carbon nucleophiles to the resulting enones, 6 --> 8 --> 9 and 9 --> 10,11 --> 13. Subsequent reductive desulfurization of the adducts 13 provided 14 in good overall yield from 1. Bicyclic ketones 14 are envisioned as promising intermediates for natural product synthesis. As examples, syntheses of two elemanoid sesquiterpenes, beta-elemenone (16) and eleman-8-beta,12-olide (17) in optically active form from (1R,4S,5S)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one (14a) were carried out.
• Preparation of Optically Active Apoverbenone and Verbenone from Nopinone by Use of the Sulfenylation−Dehydrosulfenylation Method. Stability and Reactivity Attributable to Absolute Configuration at the Sulfur Atom in Sulfoxides
  作者：Hiroshi Kosugi、Jaseung Ku、Michiharu Kato

  DOI：10.1021/jo9807316

  日期：1998.10.1

  with 19a. As a result, it was proved that, in 3-(phenylsulfinyl)nopinones, thermodynamic stability of isomers is dependent on absolute configuration at the sulfur center; that is, the trans-isomer 10a possesses an R(s)-phenylsulfinyl group and the cis-isomer 10b possesses an S(s)-phenylsulfinyl group, and it was proved that, in (4R)-4-methyl-3-(phenylsulfinyl)nopinones, both cis-isomers 18a,b are stable

  旋光形式的Apoverbenone（4）和verbenone（5）作为对映选择性合成中的手性来源，可能是有用的化合物。以易于从（-）-β-pine烯，（+）-apoverbenone（4a）和（+）-verbenone（5a）购得的（+）-nopinone（1）开始，以合成上令人满意的总收率制备，通常使用亚磺酰化-脱氢亚磺酰化方法涉及烯酮官能团的构建。该方法学可适用于从（-）-去甲酮开始制备其对映体（-）-4b和（-）-5b。虽然亚砜10a，b和18a，b中的苯亚磺酰基的构型是通过（1）H NMR光谱和NOE相关性确定的，但通过在（1）H NMR光谱中比较它们的同系物，可以得出硫原子的绝对构型绝对配置明确的 即10a与13a，10b与13b，18a与19b和18b与19a。结果证明，在3-（苯基亚磺酰基）nopinones中，异构体的热力学稳定性取决于硫中心的绝对构型；即，反式异构体10a