(1R,3R,6R,7S,8R,9R)-7-acetyl-11,11-dimethyl-6-vinyl-2,10,12-trioxatricyclo<7.3.0.0^3,8>dodecane | 142133-29-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,3R,6R,7S,8R,9R)-7-acetyl-11,11-dimethyl-6-vinyl-2,10,12-trioxatricyclo<7.3.0.0^3,8>dodecane
• 英文别名: 1-[(3aR,4aR,7R,8S,8aR,8bR)-7-ethenyl-2,2-dimethyl-3a,4a,5,6,7,8,8a,8b-octahydro-[1,3]dioxolo[4,5-b][1]benzofuran-8-yl]ethanone
• CAS: 142133-29-7
• 化学式: C₁₅H₂₂O₄
• 分子量: 266.337
• InChiKey: AZBUPEFOIHQWRY-XNBXPENISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3-C-acetylmethyl-3-deoxy-1,2-O-isopropylidene-α-D-allofuranose 在 Raney nickel T-4 4-二甲氨基吡啶 、 sodium periodate 、 lithium aluminium tetrahydride 、 4 A molecular sieve 、 氢气 、 sodium hydride 、 二异丁基氢化铝 、 对甲苯磺酰氯 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， -70.0~25.0 ℃ 、101.33 kPa 条件下， 反应 59.5h， 生成 (1R,3R,6R,7S,8R,9R)-7-acetyl-11,11-dimethyl-6-vinyl-2,10,12-trioxatricyclo<7.3.0.0^3,8>dodecane
  参考文献：
  名称：

  Tandem intramolecular Michael addition/aldol condensation or acylation applied to D-glucose-derived substrates: preparation of enantiomeric octahydronaphthalenone derivatives equipped with C- and O-functionalities

  摘要：

  An enantiomerically pure (1,2-isopropylidenedioxy)tetrahydrofuran derivative, 9, bearing acetonyl and propionaldehyde side chains smoothly underwent aldol cyclization under basic conditions. The major product was the cis-aldol 21S, accompanied by the trans-diastereomer 21R in a ratio of 4 to 1. Further functionalized substrates 10 and 11, with either a (4-acetyl)- or a (4-ethoxycarbonyl)-3(E)-butenyl group, smoothly underwent a tandem Michael addition/aldol condensation or acylation by treatment with sodium hydride (NaH). In the case of 10, two cis-fused octahydronaphthalenones, 23 and 25, and a trans-fused diasteromer, 24, were isolated in 20%, 33%, and 11% yields, respectively. The substrate 11 provided a cis-substituted perhydrobenzofuran derivative, 26, and cis- and trans-fused octahydronaphthalenediones, 27 and 28, in 52%, 17%, and 9% yields, respectively. An intramolecular S(N)2' type cyclization of the corresponding 5-chloro-3(E)-pentenyl derivative, 14, provided exclusively (96%) the perhydrobenzofuran derivative, 29, in which the two newly introduced substituents are disposed in a cis relationship. The stereochemical assignments for each cyclization product were achieved by H-1 NMR analysis of the cyclization products or their chemically modified compounds. Preferential formation of the cis-fused carbocycles in the present studies is rationalized from a stereoelectronic viewpoint. Furthermore, the effect of substituents on the cyclization was investigated using two tetrahydrofuran derivatives, 20S and 20R. Base treatment of 20S gave the cis-fused tandem cyclization product 30 and the trans diastereomer 31 in a ratio of 3.8 to 1. In contrast, 20R gave two cyclization products, 32 and 33, in a ratio of 5 to 1, as a result of a preferential trans cyclization mode.

  DOI：

  10.1021/jo00042a034

文献信息

• Tandem intramolecular Michael addition/aldol condensation or acylation applied to D-glucose-derived substrates: preparation of enantiomeric octahydronaphthalenone derivatives equipped with C- and O-functionalities
  作者：Kinichi Tadano、Kensuke Nagashima、Yoshihide Ueno、Seiichiro Ogawa

  DOI：10.1021/jo00042a034

  日期：1992.7

  An enantiomerically pure (1,2-isopropylidenedioxy)tetrahydrofuran derivative, 9, bearing acetonyl and propionaldehyde side chains smoothly underwent aldol cyclization under basic conditions. The major product was the cis-aldol 21S, accompanied by the trans-diastereomer 21R in a ratio of 4 to 1. Further functionalized substrates 10 and 11, with either a (4-acetyl)- or a (4-ethoxycarbonyl)-3(E)-butenyl group, smoothly underwent a tandem Michael addition/aldol condensation or acylation by treatment with sodium hydride (NaH). In the case of 10, two cis-fused octahydronaphthalenones, 23 and 25, and a trans-fused diasteromer, 24, were isolated in 20%, 33%, and 11% yields, respectively. The substrate 11 provided a cis-substituted perhydrobenzofuran derivative, 26, and cis- and trans-fused octahydronaphthalenediones, 27 and 28, in 52%, 17%, and 9% yields, respectively. An intramolecular S(N)2' type cyclization of the corresponding 5-chloro-3(E)-pentenyl derivative, 14, provided exclusively (96%) the perhydrobenzofuran derivative, 29, in which the two newly introduced substituents are disposed in a cis relationship. The stereochemical assignments for each cyclization product were achieved by H-1 NMR analysis of the cyclization products or their chemically modified compounds. Preferential formation of the cis-fused carbocycles in the present studies is rationalized from a stereoelectronic viewpoint. Furthermore, the effect of substituents on the cyclization was investigated using two tetrahydrofuran derivatives, 20S and 20R. Base treatment of 20S gave the cis-fused tandem cyclization product 30 and the trans diastereomer 31 in a ratio of 3.8 to 1. In contrast, 20R gave two cyclization products, 32 and 33, in a ratio of 5 to 1, as a result of a preferential trans cyclization mode.