N-[(1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)cyclohex-2-enyl]-2,2,2-trichloroacetamide | 951345-91-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-[(1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)cyclohex-2-enyl]-2,2,2-trichloroacetamide
• 英文别名: N-[(1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)cyclohex-2-en-1-yl]-2,2,2-trichloroacetamide
• CAS: 951345-91-8
• 化学式: C₁₄H₂₁BrCl₃NO₇
• 分子量: 501.586
• InChiKey: DRWWGKNMJGJMIJ-NOOOWODRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  26
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  84.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  N-[(1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)cyclohex-2-enyl]-2,2,2-trichloroacetamide 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 0.25h， 以89%的产率得到(1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)-cyclohex-2-enamine
  参考文献：
  名称：

  Chemoenzymatic Approaches to Lycorine-Type Amaryllidaceae Alkaloids:  Total Syntheses of ent-Lycoricidine, 3-epi-ent-Lycoricidine, and 4-Deoxy-3-epi-ent-lycoricidine

  摘要：

  The readily available and enzymatically derived cis-1,2-dihydrocatechol 4 has been elaborated, over 11 steps including an Overman rearrangement, into the non-natural enantiomer, (-)-1, of the alkaloid lycoricidine [(+)-1]. Related chemistries have provided analogues 18, 19, and 26.

  DOI：

  10.1021/ol701552r
• 作为产物：
  描述：

  (3aS,4R,5R,7aS)-7-bromo-4,5-bis(methoxymethoxy)-2-(4-methoxyphenyl)-3a,4,5,7a-tetrahydrobenzo[d][1,3]dioxole 在 水 、 sodium hydride 、 二异丁基氢化铝 、 potassium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 、 邻二氯苯 、 甲苯 为溶剂， 反应 38.0h， 生成 N-[(1R,4R,5S,6R)-2-bromo-4,5,6-tris(methoxymethoxy)cyclohex-2-enyl]-2,2,2-trichloroacetamide
  参考文献：
  名称：

  Chemoenzymatic Approaches to Lycorine-Type Amaryllidaceae Alkaloids:  Total Syntheses of ent-Lycoricidine, 3-epi-ent-Lycoricidine, and 4-Deoxy-3-epi-ent-lycoricidine

  摘要：

  The readily available and enzymatically derived cis-1,2-dihydrocatechol 4 has been elaborated, over 11 steps including an Overman rearrangement, into the non-natural enantiomer, (-)-1, of the alkaloid lycoricidine [(+)-1]. Related chemistries have provided analogues 18, 19, and 26.

  DOI：

  10.1021/ol701552r

文献信息

• The Regio- and Stereo-Selective Formation of Allylic Chlorides During the Overman Rearrangement of Trichloroacetimidates Derived from Certain Brominated Conduritols
  作者：Maria Matveenko、Anthony C. Willis、Martin G. Banwell

  DOI：10.1071/ch08438

  日期：——

  Microwave irradiation of imidate 2 at 165°C affords a ~3:1 mixture of the Overman rearrangement product 3 and the allylic chloride 4 (83% combined yield). Under the same conditions the deoxy-conduritol 6 gives a comparable mixture of compounds 7 and 8. The single-crystal X-ray structure of a derivative of chloride 8 is reported together with a mechanism that accounts for the selective formation of

  亚氨酸酯2在165°C的微波辐射下，Overman重排产物3和烯丙基氯4的混合物比例约为3：1 （总产率为83％）。在相同条件下，脱氧-高糖醇6得到化合物7和8的可比混合物。报道了氯化物8的衍生物的单晶X射线结构以及解释该化合物和同类物4选择性形成的机理。
• A chemoenzymatic total synthesis of ent-narciclasine
  作者：Maria Matveenko、Martin G. Banwell、Anthony C. Willis

  DOI：10.1016/j.tet.2008.01.113

  日期：2008.5

  The synthesis of the title compound [(-)-1] has been achieved, for the first time, by reacting the aryl boronic acid ester 4 with the amino-conduritol derivative 6 under Suzuki-Miyaura cross-coupling conditions then subjecting the product phenanthridinone 23 to a global deprotection process using trimethylsilyl bromide. The aromatic building block 4 was prepared in ten steps from piperonal while compound 6 was obtained in nine steps from the enantiomerically pure cis-1,2-dihydrocatechol 7. This last compound is available, in multi-gram quantities, through a whole-cell-mediated biotransformation of bromobenzene using genetically engineered organisms that over-express the responsible enzyme, namely toluene dioxygenase. Since the enantiomer of compound 7 is available by related means, the present work also represents a formal total synthesis of the alkaloid narciclasine [(+)-1]. The single-crystal X-ray analysis of compound 13 is reported. (C) 2008 Elsevier Ltd. All rights reserved.