(4S*,4aS*)-4-Methyl-4,4a,5,6-tetrahydrocyclopentapyran-1(3H)-one | 123718-10-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: (4S*,4aS*)-4-Methyl-4,4a,5,6-tetrahydrocyclopentapyran-1(3H)-one
• 英文别名: (4SR,4aSR)-4-methyl-1,3,4,4a,5,6-hexahydrocyclopentaoxin-1-one；4-methyl-1,3,4,4a,5,6-hexahydrocyclopenta[c]oxin-1-one；(4S*,4aS*)-4-Methyl-4,4a,5,6-tetrahydrocyclopenta[c]pyran-1(3H)-one；(4R,4aR)-4-methyl-4,4a,5,6-tetrahydro-3H-cyclopenta[c]pyran-1-one
• CAS: 123718-10-5；123718-11-6
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: RVHJCJHLAGWVTA-NKWVEPMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.52
• 重原子数：
  11.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (4S*,4aS*)-4-Methyl-4,4a,5,6-tetrahydrocyclopentapyran-1(3H)-one 、 alkaline earth salt of/the/ methylsulfuric acid 以 乙醚 为溶剂， 以90%的产率得到4α,4aα,7α,7aα-dihydronepetalactone
  参考文献：
  名称：

  New type of cyclization of .alpha.,.beta.,.chi.,.psi.-unsaturated dioic acid esters through tandem conjugate additions by using lithium N-benzyl-N-(trimethylsilyl)amide as a nitrogen nucleophile

  摘要：

  Treatment of dimethyl (2E,6E)-2,6-octadienedioate with lithium N-benzyl-N-(trimethylsilyl)amide (LSA) gave 5-exo-trig ring closure products, methyl 3-(N-benzylamino)-2-(methoxycarbonyl)cyclopentane-1-acetates, through tandem conjugate additions. The related 6-exo-trig cyclization proceeded stereoselectively to give ethyl c-3-(N-benzylamino)-t-2-(ethoxycarbonyl)cyclohexane-1-acetate. In contrast with the 5- and 6-exo-trig cyclization, no 7-exo-trig cyclization occurred. The 5-exo-trig cyclization products were converted into 2-(methoxycarbonyl)-2-cyclopentene-1-carboxylic acid methyl ester in an excellent yield. 5-exo-trig cyclization of the unsymmetrical dienedioate consisting of crotonate and (E)-2-methyl-2-butenoate units proceeded regioselectively through conjugate addition of LSA to the crotonate part. Similar regioselectively was observed in the case of 5-exo-trig cyclization of the dienedioate possessing crotonate and (E)-3-methyl-2-pentenoate units. Total syntheses of the physiologically active cyclopentane monoterpenes (+/-)-dihydronepetalactone and (+/-)-isohydronepetalactone has been accomplished by this cyclization strategy. In addition, it has been demonstrated that LSA is a more efficient nitrogen nucleophile than LDA to cyclize omega-halo-alpha,beta-unsaturated esters.

  DOI：

  10.1021/jo00037a034
• 作为产物：
  描述：

  dimethyl (E,E)-octa-2,6-diendioate 在 manganese(IV) oxide 、 lithium aluminium tetrahydride 、 silica gel 、 potassium carbonate 作用下， 以 甲醇 、 乙醚 、 氯仿 、 xylene 为溶剂， 反应 42.5h， 生成 (4S*,4aS*)-4-Methyl-4,4a,5,6-tetrahydrocyclopentapyran-1(3H)-one
  参考文献：
  名称：

  New type of cyclization of .alpha.,.beta.,.chi.,.psi.-unsaturated dioic acid esters through tandem conjugate additions by using lithium N-benzyl-N-(trimethylsilyl)amide as a nitrogen nucleophile

  摘要：

  Treatment of dimethyl (2E,6E)-2,6-octadienedioate with lithium N-benzyl-N-(trimethylsilyl)amide (LSA) gave 5-exo-trig ring closure products, methyl 3-(N-benzylamino)-2-(methoxycarbonyl)cyclopentane-1-acetates, through tandem conjugate additions. The related 6-exo-trig cyclization proceeded stereoselectively to give ethyl c-3-(N-benzylamino)-t-2-(ethoxycarbonyl)cyclohexane-1-acetate. In contrast with the 5- and 6-exo-trig cyclization, no 7-exo-trig cyclization occurred. The 5-exo-trig cyclization products were converted into 2-(methoxycarbonyl)-2-cyclopentene-1-carboxylic acid methyl ester in an excellent yield. 5-exo-trig cyclization of the unsymmetrical dienedioate consisting of crotonate and (E)-2-methyl-2-butenoate units proceeded regioselectively through conjugate addition of LSA to the crotonate part. Similar regioselectively was observed in the case of 5-exo-trig cyclization of the dienedioate possessing crotonate and (E)-3-methyl-2-pentenoate units. Total syntheses of the physiologically active cyclopentane monoterpenes (+/-)-dihydronepetalactone and (+/-)-isohydronepetalactone has been accomplished by this cyclization strategy. In addition, it has been demonstrated that LSA is a more efficient nitrogen nucleophile than LDA to cyclize omega-halo-alpha,beta-unsaturated esters.

  DOI：

  10.1021/jo00037a034

文献信息

• Cyclisation of α,β,γ,ψ-unsaturated dioic acid esters via tandem conjugate additions by using lithium N-benzyltrimethylsilylamide (LSA) as a nitrogen nucleophile and its application to a total synthesis of (±)-dihydronepetalactone and (±)-isodihydronepetalactone
  作者：Tadao Uyehara、Naomi Shida、Yoshinori Yamamoto

  DOI：10.1039/c39890000113

  日期：——

  A stereoselective total synthesis of (±)-dihydronepetalactone and (±)-isodihydronepetalactone has been accomplished by utilising a novel cyclisation procedure; a reaction of octadiene-2,6-dioic acid esters with lithium N-benzyltrimethylsilylamide (LSA) induces 5-exo-Trig ring-closure via tandem conjugate additions.

  （±）-二氢荆芥内酯和（±）-异二氢荆芥内酯的立体选择性全合成已经通过利用新颖的环化方法完成。辛二烯-2,6-二酸酯与N-苄基三甲基甲硅烷基氨基锂（LSA）的反应通过串联共轭物加成引发5-exo-Trig闭环。
• Formal Synthesis of (±)-Isodihydronepetalactone
  作者：Meng-Yang Chang、Bo-Rm Chang、Chung-Ho Chang、Shui-Tein Chen、Nein-Chen Chang

  DOI：10.1002/jccs.200200036

  日期：2002.4

  AbstractA formal synthesis of (±)‐isodihydronepetalactone (1) from cyclobutenone 5 was de scribed. Baeyer‐Villiger lactonization of cyclobutanone 8 followed by decholorination led to lactone 4, which under went a series of functional group trans formations, furnished cyclopentanone derivative 15. Shapiro reaction on hydrazone derivative in the presence of excess dry ice gave lactone 2. Lactone 2 had previously been converted to isodihydronepetalactone (1).
• Formal Synthesis of (±)-Mitsugashiwalactone and (±)-Isodihydronepetalactone from Norborn-5-en-2-one Involving Shapiro Reaction
  作者：Meng-Yang Chang、Nein-Chen Ciang

  DOI：10.1002/jccs.199900005

  日期：1999.2

  AbstractA formal synthesis of (±)‐mitsugashiwalactone (1) and (±)‐isodihydro nepetalactone (2) was accomplished. Baeyer‐Villiger lactonization of ketone 9 followed by acidic treatment led to the rearranged lactone 8, which underwent a series of functional group transformations to give cyclopentanone derivatives 19 and 20. Shapiro reaction on 21 and 22 in the presence of excess dry ice gave lactones 5 and 6. Lactones 5 and 6 previously have been converted to mitsugashiwalactone (1) and isodihydronepetalactone (2), respectively.
• UYEHARA, TADAO;SHIDA, NAOMI;YAMAMOTO, YOSHINORI, J. CHEM. SOC. CHEM. COMMUN.,(1989) N, C. 113-114
  作者：UYEHARA, TADAO、SHIDA, NAOMI、YAMAMOTO, YOSHINORI

  DOI：——

  日期：——