ethyl (2E)-2-{(4S)-4-[(tert-butyldiphenylsilyloxy)methyl]-2,2-dimethyl-1,3-dioxan-5-ylidene}acetate | 1373934-43-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl (2E)-2-{(4S)-4-[(tert-butyldiphenylsilyloxy)methyl]-2,2-dimethyl-1,3-dioxan-5-ylidene}acetate
• 英文别名: ethyl (4S,2E)-2-{4-[(tert-butyldiphenylsilyloxy)methyl]-2,2-dimethyl-1,3-dioxan-5-ylidene}acetate
• CAS: 1373934-43-0
• 化学式: C₂₇H₃₆O₅Si
• 分子量: 468.665
• InChiKey: TUAUQDDIUSVPBH-AXCOVZPISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  33.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  ethyl (2E)-2-{(4S)-4-[(tert-butyldiphenylsilyloxy)methyl]-2,2-dimethyl-1,3-dioxan-5-ylidene}acetate 在 二异丁基氢化铝 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 0.83h， 生成
  参考文献：
  名称：

  An efficient synthesis of the polar part of sulfamisterin and its analogs

  摘要：

  An efficient synthesis of the polar part of sulfamisterin and its analogs starting from D-xylose is described. The corresponding allylic thiocyanates and trichloroacetimidates were subjected to aza-Claisen rearrangement that effectively generated a quaternary carbon having an amino group as one of the sub-stituents. Subsequent functional group interconversions afforded the highly functionalized branched aminopolyol 29 that is expected to have the crucial application in the construction of sulfamisterin. On the other hand, the second diastereoisomer 34 would be transformed to 2-epi-congener. With respect to the appropriate stereochemical arrangement, the prepared polar segments 29 and 34 can also be utilized for the synthesis of mycestericins (E, G) and their analogs. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2012.02.019
• 作为产物：
  描述：

  (4R,5R)-5-(benzyloxy)-4-(benzyloxymethyl)-2,2-dimethyl-1,3-dioxane 在 咪唑 、 palladium 10% on activated carbon 、 氢气 、 2-碘酰基苯甲酸 作用下， 以 乙醇 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 6.6h， 生成 ethyl (2E)-2-{(4S)-4-[(tert-butyldiphenylsilyloxy)methyl]-2,2-dimethyl-1,3-dioxan-5-ylidene}acetate
  参考文献：
  名称：

  An efficient synthesis of the polar part of sulfamisterin and its analogs

  摘要：

  An efficient synthesis of the polar part of sulfamisterin and its analogs starting from D-xylose is described. The corresponding allylic thiocyanates and trichloroacetimidates were subjected to aza-Claisen rearrangement that effectively generated a quaternary carbon having an amino group as one of the sub-stituents. Subsequent functional group interconversions afforded the highly functionalized branched aminopolyol 29 that is expected to have the crucial application in the construction of sulfamisterin. On the other hand, the second diastereoisomer 34 would be transformed to 2-epi-congener. With respect to the appropriate stereochemical arrangement, the prepared polar segments 29 and 34 can also be utilized for the synthesis of mycestericins (E, G) and their analogs. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2012.02.019

文献信息

• Total synthesis of mycestericin A and its 14-epimer
  作者：Hiroyoshi Yamanaka、Kazuya Sato、Hideyuki Sato、Masatoshi Iida、Takeshi Oishi、Noritaka Chida

  DOI：10.1016/j.tet.2009.09.012

  日期：2009.11

  The total synthesis of mycestericin A (1) and its 14-epimer 34 is described herein. The Overman rearrangement of an allylic trichloroacetimidate derived from l-tartrate generated a tetra-substituted carbon with nitrogen and subsequent stereoselective transformations afforded the highly functionalized left-half segment, vinyl iodide. Cross-coupling of the vinyl iodide with a chiral organometallic species

  本文描述了mycestericin A（1）及其14-受体34的总合成。衍生自1-酒石酸酯的烯丙基三氯乙酰亚胺酸酯的超载重排产生了具有氮的四取代碳，随后的立体选择性转化提供了高度官能化的左半段碘乙烯。在Negishi或Suzuki-Miyaura偶联条件下，碘化乙烯与d-酒石酸合成的手性有机金属物质交叉偶联，然后脱保护，完成了1的总合成。还合成了Mycestericin A的14个表位，并比较了[α] D霉菌素A及其14-受体的过乙酰基γ-内酯衍生物的分子量值以及对1和34的降解研究充分证实了拟议的霉菌素A的绝对结构。