(-)-(1S,4R,5R,6R)-6-endo-chloro-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one | 128573-16-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: (-)-(1S,4R,5R,6R)-6-endo-chloro-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one
• 英文别名: (-)-6-endo-chloro-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one；(-)-(1S,4R,5R,6R)-5-exo-benzeneselenyl-6-endo-chloro-7-oxabicyclo[2.2.1]heptan-2-one；(1S,4R,5R,6R)-6-chloro-5-phenylselanyl-7-oxabicyclo[2.2.1]heptan-2-one
• CAS: 128573-16-0
• 化学式: C₁₂H₁₁ClO₂Se
• 分子量: 301.631
• InChiKey: YKOCFQWJXOELLE-WISYIIOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.15
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-(1S,4R,5R,6R)-6-endo-chloro-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one 在 氢气 、 sodium acetate 、 碳酸氢钠 、 sodium carbonate 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 105.58h， 生成 (-)-(1S,4S,5S,7S)-7-endo-chloro-3-oxo-2,8-dioxabicyclo<3.2.1>oct-4-exo-yl metachlorobenzoate
  参考文献：
  名称：

  Total asymmetric syntheses of d-lividosamine and 2-acetamido-2,3-dideoxy-d-arabino-hexose derivatives.

  摘要：

  DOI：

  10.1016/s0040-4020(01)88357-5
• 作为产物：
  描述：

  (+)-(1R,4R)-7-oxabicyclo<2.2.1>-hept-5-en-2-one 、 苯基氯化硒 以 氯仿 为溶剂， 反应 0.25h， 生成 (-)-(1S,4R,5R,6R)-6-endo-chloro-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1]heptan-2-one
  参考文献：
  名称：

  The electron-releasing homoconjugated carbonyl group. Application to the total syntheses of 3-deoxy-, 4-deoxy-hexose, lividosamine and derivatives

  摘要：

  DOI：

  10.1016/s0040-4039(00)70712-x

文献信息

• Asymmetric Syntheses of New Polyhydroxylated Quinolizidines: Cross-Aldol Reactions of 7-Oxabicyclo[2.2.1]heptan-2-one and 3a,4a,7a,7b-Tetrahydro[1,3]dioxolo[4,5]furo[2,3-d]isoxazole-3-carbaldehyde Derivatives
  作者：Christophe Schaller、Pierre Vogel

  DOI：10.1002/(sici)1522-2675(20000119)83:1<193::aid-hlca193>3.0.co;2-i

  日期：2000.1.19

  Protocols were found for highly diastereoselective condensation giving the four possible aldols (+)-27 ('anti'), (+)-28 ('syn). 29 ('anti'). and (-)-30 ('syn') resulting from the exclusive exo-face reaction of the bicyclic lithium enolate of (-)-25 and bicyclic silyl ether (-)-31. Steric factors can explain the selectivities observed. Aldols (+)-27 (+)-28, 29, and (-)-30 were converted stereoselectively

  (-)-(1S,4R,5R,6R)-6-endo-chloro-5-exo-(phenylseleno)-7-oxabicyclo[2.2.1] heptan-2-one ((-) -25) 和 (+)-(3aR,4aR,7aR,7bS)- ((+)-26) 和 (-)-(3aS,4aS,7aS,7bR)-3a,4a,7a,7b-四氢-6,6-dimethyl[1,3]dioxolo [4,5]furo[2,3-d]isoxazole-3-carbaldehyde ((-)-26) 用于 (-)-25 的烯醇锂和在 Mukaiyama 的条件下，它的三甲基甲硅烷基醚 (-)-31 (Scheme 2)。发现了高度非对映选择性缩合的协议，给出了四种可能的醛醇 (+)-27 ('anti')、(+)-28 ('syn)。29（“反”）。和 (-)-30 ('syn') 由 (-)-25 的双环烯醇锂和双环甲硅烷基醚
• Synthesis of C-Linked Imino Disaccharides (= Aza-C-disaccharides) with a Pyrrolidine-3,4-diol Moiety Attached at C(3) of Galactosevia a Hydroxymethylene Linker and of a 7-(1,2,3-Trihydroxypropyl)-octahydroxyindolizine-1,2,6,8-tetrol
  作者：Karin Kraehenbuehl、Sylviane Picasso、Pierre Vogel

  DOI：10.1002/hlca.19980810552

  日期：——

  deoxy-2,6-bis-O-(methoxymethyl)-α-DL-galactopyranose (54). Clean oxidation of the furan unit in (54). Clean oxidation of the furan unit in 54 was possible with dimethyldioxirane, giving the corresponding (Z)-4-oxoenal 59 that was converted into pyrroles such as (±)-1,4-anhydro-3-(SR)-[(tert-butyl)dimethylsilyloxy](1-benzyl-1 H-pyrrol-2-yl)methyl}-3-deoxy-2,6-bis-O-(methoxymethyl)-α-DL-galactopyranose

  将（±）-6-内-氯-5-外-（苯基硒代）-7-氧杂双环[2.2.1]庚二-2-酮（16）的烯醇锂添加到呋喃-2-甲醛中得到单个羟醛19（方案1和2）以高立体选择性转化为（±）-（1 RS，3 SR，4 SR，5 RS，6 SR）-5- exo -（RS）-[（叔丁基）二甲基甲硅烷氧基]（呋喃-2-基）甲基} -6-内-（甲氧基甲氧基）-2-氧代-7-氧杂双环[2.2.1]庚-3-外基-4-溴苯磺酸盐（46）。高度选择性拜尔-维利格氧化46提供了相应的β-DL-altrofuranurono -6,1-内酯49，甲醇分解，其中，得到（±） -甲基1,5-脱水-3 - （SR） - 〔（叔-丁基）二甲基甲硅烷氧基]（呋喃-2-基）甲基} -3-脱氧-2- O-（甲氧基甲基）-α-DL-半呋喃呋喃酸酯（51）。还原51，然后提供保护，提供（±）-1,4-脱水-3-（SR）-[（叔丁基）二甲基甲硅烷氧基]（呋喃-2-基）甲基}
• The electron-releasing homoconjugated carbonyl group. Application to the total syntheses of 3-deoxy-, 4-deoxy-hexose, lividosamine and derivatives
  作者：Daniela Fattori、Etienne de Guchteneere、Pierre Vogel

  DOI：10.1016/s0040-4039(00)70712-x

  日期：1989.1
• Synthesis of a Polyhydroxyquinolizidine bearing a Polyhydroxylated Carbon Side-Chain
  作者：Christophe Schaller、Pierre Vogel

  DOI：10.1055/s-1999-3164

  日期：1999.8
• Synthesis of Undeculofuranoside Derivatives of the Herbicidins and of Analogs
  作者：Fabienne Emery、Pierre Vogel

  DOI：10.1021/jo00123a021

  日期：1995.9

  The condensation of 3-O-(tert-butyldimethylsilyl)-5-deoxy-1,2-O-isopropylidene-alpha-D-xylo-hexodialdo-1,4-furanose (obtained in six steps (35%) from D-glucurono-6,3-lactone) with the lithium enolate of (+/-)6-endo-chloro-5-endo-(methoxymethoxy)-7-oxabicyclo[2.2.1]heptan-2-one (derived in six steps (25%) from the Diels-Alder adduct of furan to 1-cyanovinyl acetate) was highly exo face selective giving two major aldols that were separated readily. One of them was converted to 6,10-anhydro-5-deoxy-1,2-O-isopropylidene-9-O-(methoymethyl)-alpha-D-arabino-L-ido-7-undeculofuranose-(1,4)-pyranose-(7,3), a semiprotected form of the long-chain carbohydrate moiety of the herbicidins. The synthesis implies the acid-promoted isomerization of 10,11-anhydro-5,7-dideoxy-1,2-O-isopropylidene-9-O-(methoxymethyl)-7-C-[(2-nitrophenyl)selenomethyl]-beta-L-ido-L-ido-undecofuranose.