(2R^*,3aR^*,7aR^*)-hexahydro-2-<(benzoyloxy)methyl>-4(2H)-benzofuranone | 134134-40-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R^*,3aR^*,7aR^*)-hexahydro-2-<(benzoyloxy)methyl>-4(2H)-benzofuranone
• 英文别名: (2R^*,3aR^*,7aR^*)-hexahydro-2-[(benzoyloxy)methyl]-4(2H)-benzofuranone；[(2R,3aR,7aR)-4-oxo-3,3a,5,6,7,7a-hexahydro-2H-1-benzofuran-2-yl]methyl benzoate
• CAS: 134134-40-0
• 化学式: C₁₆H₁₈O₄
• 分子量: 274.317
• InChiKey: MWKFDNJGHWIIIQ-VNHYZAJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R^*,3aR^*,7aR^*)-hexahydro-2-<(benzoyloxy)methyl>-4(2H)-benzofuranone 在 吡啶 、 臭氧 、 间氯过氧苯甲酸 、 lithium hexamethyldisilazane 作用下， 以 二氯甲烷 为溶剂， 反应 73.33h， 生成 (3aR*,8aR*)-2(R*)-<(Benzoyloxy)methyl>-5-oxo-3a,5,8,8a-(tetrahydro)tetrahydrofuro<3,2-b>oxepin
  参考文献：
  名称：

  General approach to halogenated tetrahydrofuran natural products from red algae of the genus Laurencia. Total synthesis of (.+-.)-kumausallene and (.+-.)-1-epi-kumausallene

  摘要：

  An efficient, stereocontrolled entry to the dioxabicyclo[3.3.0]octane ring system of (+/-)-kumausallene has been developed. This synthesis builds upon our general strategy for preparing C-15 halogenated tetrahydrofuranoid marine lipids using the ring-enlarging tetrahydrofuran annulation of cyclic, allylic diols as the central step. The key intermediate, hydrobenzofuranone 8, is available with complete stereocontrol from the Lewis acid-catalyzed condensation of 1-vinylcyclopentanediol (4) and alpha-(benzoyloxy)acetaldehyde(Scheme II). Elaboration of 8 into the bicyclic ring system of 13 requires only four steps and proceeds with excellent stereocontrol in 41% overall yield. The total synthesis of (+/-)-kumausallene from 8 is accomplished in 17 steps and 2% overall yield. As a corollary, the total synthesis of (+/-)-1-epi-kumausallene confirms the stereochemical assignment for the bromoallene moiety of the natural product.

  DOI：

  10.1021/jo00061a021
• 作为产物：
  描述：

  环辛烷-1,2-二酮 在 sodium tetrahydroborate 、 三氟化硼乙醚 、 溶剂黄146 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 0.42h， 生成 (2R^*,3aR^*,7aR^*)-hexahydro-2-<(benzoyloxy)methyl>-4(2H)-benzofuranone
  参考文献：
  名称：

  环状烯丙基二醇与羰基化合物的酸促进反应。立体选择性扩环四氢呋喃环化

  摘要：

  各种顺式稠合六氢环戊 [b] 呋喃 4-酮 (3, n=0)、六氢 4(2H)-苯并呋喃酮 (3, n=1) 和八氢环庚 [b] 呋喃 4-酮(3, n=2) 可以通过标题反应以高水平的立体控制制备。详细探讨了这种用于组装多环醚的强大新方法的范围和局限性。潜在的氧杂双环 [4.4.0] 癸基、氧杂双环 [4.3.0] 壬基和氧杂双环 [4.2.0] 辛基阳离子中间体的构象分析可以预测标题反应的立体化学结果

  DOI：

  10.1021/ja00014a031

文献信息

• Acid-promoted reaction of cyclic allylic diols with carbonyl compounds. Stereoselective ring-enlarging tetrahydrofuran annulations
  作者：Mark J. Brown、Timothy Harrison、Paul M. Herrinton、Mark H. Hopkins、Kira D. Hutchinson、Larry E. Overman、Pratibha Mishra

  DOI：10.1021/ja00014a031

  日期：1991.7

  high levels of stereocontrol by the title reaction. The scope and limitations of this powerful new method for assembling polycyclic ethers are explored in detail. Conformational analysis of potential oxabicyclo [4.4.0] decanyl, oxabicyclo [4.3.0] nonanyl, and oxabicyclo [4.2.0] octanyl cation intermediates allows the stereochemical outcome of the title reaction to be predicted

  各种顺式稠合六氢环戊 [b] 呋喃 4-酮 (3, n=0)、六氢 4(2H)-苯并呋喃酮 (3, n=1) 和八氢环庚 [b] 呋喃 4-酮(3, n=2) 可以通过标题反应以高水平的立体控制制备。详细探讨了这种用于组装多环醚的强大新方法的范围和局限性。潜在的氧杂双环 [4.4.0] 癸基、氧杂双环 [4.3.0] 壬基和氧杂双环 [4.2.0] 辛基阳离子中间体的构象分析可以预测标题反应的立体化学结果
• General approach to halogenated tetrahydrofuran natural products from red algae of the genus Laurencia. Total synthesis of (.+-.)-kumausallene and (.+-.)-1-epi-kumausallene
  作者：Timothy A. Grese、Kira D. Hutchinson、Larry E. Overman

  DOI：10.1021/jo00061a021

  日期：1993.4

  An efficient, stereocontrolled entry to the dioxabicyclo[3.3.0]octane ring system of (+/-)-kumausallene has been developed. This synthesis builds upon our general strategy for preparing C-15 halogenated tetrahydrofuranoid marine lipids using the ring-enlarging tetrahydrofuran annulation of cyclic, allylic diols as the central step. The key intermediate, hydrobenzofuranone 8, is available with complete stereocontrol from the Lewis acid-catalyzed condensation of 1-vinylcyclopentanediol (4) and alpha-(benzoyloxy)acetaldehyde(Scheme II). Elaboration of 8 into the bicyclic ring system of 13 requires only four steps and proceeds with excellent stereocontrol in 41% overall yield. The total synthesis of (+/-)-kumausallene from 8 is accomplished in 17 steps and 2% overall yield. As a corollary, the total synthesis of (+/-)-1-epi-kumausallene confirms the stereochemical assignment for the bromoallene moiety of the natural product.