(4S,5R,6S,10R)-4-(tert-butyldimethylsilyloxy)-5,6-epoxy-10-methyloxecane-2,7-dione | 1195113-81-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (4S,5R,6S,10R)-4-(tert-butyldimethylsilyloxy)-5,6-epoxy-10-methyloxecane-2,7-dione
• 英文别名: (1R,2S,6R,10S)-2-[tert-butyl(dimethyl)silyl]oxy-6-methyl-5,11-dioxabicyclo[8.1.0]undecane-4,9-dione
• CAS: 1195113-81-5
• 化学式: C₁₆H₂₈O₅Si
• 分子量: 328.481
• InChiKey: SMNDFZJTOGSZJM-BQPHKTIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.83
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (4S,5R,6S,10R)-4-(tert-butyldimethylsilyloxy)-5,6-epoxy-10-methyloxecane-2,7-dione 在 2-叠氮丙二酸二甲酯 、 Rh₂(OAc)4 、 氟化氢吡啶 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 2.0h， 生成 (+)-cephalosporolide B
  参考文献：
  名称：

  Cephalosporolide B Serving as a Versatile Synthetic Precursor: Asymmetric Biomimetic Total Syntheses of Cephalosporolides C, E, F, G, and (4-OMe-)G

  摘要：

  Cephalosporolide B (Ces-B) was efficiently synthesized and exploited for the first time as a versatile biomimetic synthetic precursor for the chemical syntheses of not only cephalosporolides C, G, and (4-OMe-) G via a challenging diastereoselective oxa-Michael addition but also the structurally unprecedented cephalosporolides E and F via a novel biomimetic ring-contraction rearrangement. These findings provide the first direct chemical evidence that Ces-B may be the true biosynthetic precursor of cephalosporolides.

  DOI：

  10.1021/ol402913m
• 作为产物：
  描述：

  (2R,4aS,8aS)-4a-hydroxy-2-methyl-3,4,4a,8a-tetrahydrobenzo-1(2H)-pyran-7 (8)-one 在 咪唑 、 4-二甲氨基吡啶 、 cerium(III) chloride heptahydrate 、 氨 、 sodium acetate 、 间氯过氧苯甲酸 、 三苯基膦 、 pyridinium chlorochromate 、 偶氮二甲酸二乙酯 作用下， 以 甲醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 2.0h， 生成 (4S,5R,6S,10R)-4-(tert-butyldimethylsilyloxy)-5,6-epoxy-10-methyloxecane-2,7-dione
  参考文献：
  名称：

  Cephalosporolide B Serving as a Versatile Synthetic Precursor: Asymmetric Biomimetic Total Syntheses of Cephalosporolides C, E, F, G, and (4-OMe-)G

  摘要：

  Cephalosporolide B (Ces-B) was efficiently synthesized and exploited for the first time as a versatile biomimetic synthetic precursor for the chemical syntheses of not only cephalosporolides C, G, and (4-OMe-) G via a challenging diastereoselective oxa-Michael addition but also the structurally unprecedented cephalosporolides E and F via a novel biomimetic ring-contraction rearrangement. These findings provide the first direct chemical evidence that Ces-B may be the true biosynthetic precursor of cephalosporolides.

  DOI：

  10.1021/ol402913m

文献信息

• Regioselective and Stereospecific Copper-Catalyzed Deoxygenation of Epoxides to Alkenes
  作者：Jingxun Yu、Yu Zhou、Zhenyang Lin、Rongbiao Tong

  DOI：10.1021/acs.orglett.6b02405

  日期：2016.9.16

  diazo malonate for chemo-/regioselective and stereospecific deoxygenation of various epoxides with tolerance of common functional groups (alkene, ketone, ester, p-methoxybenzyl, benzyl, tert-butyldimethylsilyl, and triisopropylsilyl). In particular, the unprecedented regioselectivity allowed for the first time monodeoxygenation of diepoxides to alkenyl epoxides. Density functional theory mechanistic studies

  两种铜盐（Cu（CF 3 CO 2）2和IMesCuCl）被鉴定为是地球上丰富的，廉价的但有效的金属催化剂，与重氮丙二酸酯一起用于各种环氧化物的化学/区域选择性和立体定向脱氧反应，并具有常见的官能团耐受性（烯烃，酮，酯，对甲氧基苄基，苄基，叔丁基二甲基甲硅烷基和三异丙基甲硅烷基）。特别是，空前的区域选择性使二环氧化物首次单脱氧为烯基环氧化物。密度泛函理论的机理研究表明，脱氧是通过折叠游离的叶立德而发生的，不利于通过可能的氧杂环丁烷的环还原而产生的直观途径。
• Concise Enantioselective Synthesis of the Ten-Membered Lactone Cephalosporolide G and Its C-3 Epimer
  作者：Silvia Barradas、Antonio Urbano、M. Carmen Carreño

  DOI：10.1002/chem.200901735

  日期：2009.9.21

  One, two, three selective oxidations are the key steps in the atom‐economic first total synthesis of the natural ten‐membered lactone cephalosporolide G and its C‐3 epimer (see scheme). They have been synthesised in only seven or eight steps starting from the natural phenol (R)‐rhododendrol, which contains all the carbon atoms present in the final targets.

  一，二，三个选择性氧化是天然的十元内酯头孢菌素G及其C-3差向异构体的原子经济首次全合成的关键步骤（参见方案）。从天然酚（R）-杜鹃醇开始，仅需七个或八个步骤即可合成它们，其中包含最终靶标中存在的所有碳原子。
• Cephalosporolide B Serving as a Versatile Synthetic Precursor: Asymmetric Biomimetic Total Syntheses of Cephalosporolides C, E, F, G, and (4-OMe-)G
  作者：Liyan Song、Yuan Liu、Rongbiao Tong

  DOI：10.1021/ol402913m

  日期：2013.11.15

  Cephalosporolide B (Ces-B) was efficiently synthesized and exploited for the first time as a versatile biomimetic synthetic precursor for the chemical syntheses of not only cephalosporolides C, G, and (4-OMe-) G via a challenging diastereoselective oxa-Michael addition but also the structurally unprecedented cephalosporolides E and F via a novel biomimetic ring-contraction rearrangement. These findings provide the first direct chemical evidence that Ces-B may be the true biosynthetic precursor of cephalosporolides.