(3aR,6R)-6-methyl-8-[tri(isopropyl)-silanyloxy]-3,3a,6,7-tetrahydrocyclohepta[c]furan-1-one | 860480-94-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3aR,6R)-6-methyl-8-[tri(isopropyl)-silanyloxy]-3,3a,6,7-tetrahydrocyclohepta[c]furan-1-one
• 英文别名: (3aR,6R)-6-methyl-8-tri(propan-2-yl)silyloxy-3,3a,6,7-tetrahydrocyclohepta[c]furan-1-one
• CAS: 860480-94-0
• 化学式: C₁₉H₃₂O₃Si
• 分子量: 336.547
• InChiKey: ATPZXOBGBIBCQJ-HOTGVXAUSA-N

物化性质

• 沸点：
  402.8±45.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3aR,6R)-6-methyl-8-[tri(isopropyl)-silanyloxy]-3,3a,6,7-tetrahydrocyclohepta[c]furan-1-one 在 臭氧 、 甲酸 、 双氧水 作用下， 以 甲醇 为溶剂， 反应 30.0h， 生成 (R)-(+)-甲基丁二酸
  参考文献：
  名称：

  Enantioselective intramolecular cyclopropanation of allyl 2-diazo-3-silanyloxybut-3-enoates

  摘要：

  The performance of the [Rh-2{(S)-ntt}(4)]-catalyst in comparison to [Rh-2{(S)-ptt}(4)] and [Rh-2{(S)-dosp},(4)] has been examined with allyl 2-diazo-3-silanvloxybut-3-enoates. The best results were obtained with [Rh-2{(S)-ptt}(4)], where enantioselectivity culminated at 89% ee at -78 degrees C. [Rh-2{(S)-ntt}(4)] was slightly less selective, while [Rh-2{(S)-dosp}(4)] was found less suitable for these substrates. However, even the results obtained with [Rh-2{(S)-pttl}(4)] are much less satisfactory than those for the intramolecular cyclopropanation of allyl diazoacetates in the presence of [Rh-2{(S)-mepy}(4)]. (c) 2005 Elsevier Ltd. Ail rights reserved.

  DOI：

  10.1016/j.tetasy.2005.04.006
• 作为产物：
  描述：

  (E,E)-(hexa-2,4-dienyl)-3-oxo-butyrate 在 [Rh₂{(S)-N-phthaloyl-tert-leucinate}4] 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 5.0h， 生成 (3aR,6R)-6-methyl-8-[tri(isopropyl)-silanyloxy]-3,3a,6,7-tetrahydrocyclohepta[c]furan-1-one
  参考文献：
  名称：

  Enantioselective intramolecular cyclopropanation of allyl 2-diazo-3-silanyloxybut-3-enoates

  摘要：

  The performance of the [Rh-2{(S)-ntt}(4)]-catalyst in comparison to [Rh-2{(S)-ptt}(4)] and [Rh-2{(S)-dosp},(4)] has been examined with allyl 2-diazo-3-silanvloxybut-3-enoates. The best results were obtained with [Rh-2{(S)-ptt}(4)], where enantioselectivity culminated at 89% ee at -78 degrees C. [Rh-2{(S)-ntt}(4)] was slightly less selective, while [Rh-2{(S)-dosp}(4)] was found less suitable for these substrates. However, even the results obtained with [Rh-2{(S)-pttl}(4)] are much less satisfactory than those for the intramolecular cyclopropanation of allyl diazoacetates in the presence of [Rh-2{(S)-mepy}(4)]. (c) 2005 Elsevier Ltd. Ail rights reserved.

  DOI：

  10.1016/j.tetasy.2005.04.006

文献信息

• <b>Asymmetric Cyclopropanations and Cycloadditions of Dioxocarbenes</b>
  作者：Paul Müller、Yves Allenbach、Sabrina Chappellet、Ashraf Ghanem

  DOI：10.1055/s-2006-926452

  日期：2006.5

  Methods for enantioselective transfer of carbenes starting from precursors carrying two carbonyl groups have been elaborated. A one-pot procedure for olefin cyclopropanation with CH-acidic precursors via intermediate phenyliodonium ylides has been developed. The structure of the [Rh2(S)-nttl}4] catalyst was optimized to produce up to 98% ee in olefin cyclopropanations with dimethyl malonate or Meldrum's

  已经详细阐述了从带有两个羰基的前体开始的对映选择性转移卡宾的方法。已经开发了一种通过中间体苯基碘叶立德与 CH-酸性前体进行烯烃环丙烷化的一锅法。[Rh2(S)-nttl}4] 催化剂的结构经过优化，可在与丙二酸二甲酯或 Meldrum 酸的烯烃环丙烷化反应中产生高达 98% 的 ee。用 (甲硅烷氧基-乙烯基) 重氮乙酸甲酯代替重氮乙酰乙酸甲酯后，可以观察到高选择性 Rh(II) 催化的烯烃环丙烷化反应。重氮丙酮酸与极性烯烃的对映选择性偶极环加成反应已通过 Ru(II)-pybox 催化剂实现。