((3aR,4aR,7R,8S,8aR,8bR)-8-Acetyl-2,2-dimethyl-octahydro-benzo[4,5]furo[2,3-d][1,3]dioxol-7-yl)-acetaldehyde | 142133-41-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((3aR,4aR,7R,8S,8aR,8bR)-8-Acetyl-2,2-dimethyl-octahydro-benzo[4,5]furo[2,3-d][1,3]dioxol-7-yl)-acetaldehyde
• 英文别名: 2-[(3aR,4aR,7R,8S,8aR,8bR)-8-acetyl-2,2-dimethyl-3a,4a,5,6,7,8,8a,8b-octahydro-[1,3]dioxolo[4,5-b][1]benzofuran-7-yl]acetaldehyde
• CAS: 142133-41-3
• 化学式: C₁₅H₂₂O₅
• 分子量: 282.337
• InChiKey: RQAWYZHGHRUUSI-UYYXNEDZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ((3aR,4aR,7R,8S,8aR,8bR)-8-Acetyl-2,2-dimethyl-octahydro-benzo[4,5]furo[2,3-d][1,3]dioxol-7-yl)-acetaldehyde 在 palladium on activated charcoal 吡啶 、 lithium aluminium tetrahydride 、 氢气 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 间氯过氧苯甲酸 作用下， 生成 Acetic acid (3aR,4aR,7S,8S,8aS,8bR)-7-(4-acetoxy-butyl)-2,2-dimethyl-octahydro-benzo[4,5]furo[2,3-d][1,3]dioxol-8-yl ester
  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
• 作为产物：
  描述：

  (1R,3R,6R,7S,8R,9R)-7-acetyl-6-<(ethoxycarbonyl)methyl>-11,11-dimethyl-2,10,12-trioxatricyclo<7.3.0.0^3,8>dodecane 在 lithium aluminium tetrahydride 作用下， 生成 ((3aR,4aR,7R,8S,8aR,8bR)-8-Acetyl-2,2-dimethyl-octahydro-benzo[4,5]furo[2,3-d][1,3]dioxol-7-yl)-acetaldehyde
  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.