(R,R)-1,3-二(4-溴苄基)-2-氯八氢-2-(2E)-巴豆基-1H-1,3,2-苯并二氮杂硅杂环戊烷 | 804559-39-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (R,R)-1,3-二(4-溴苄基)-2-氯八氢-2-(2E)-巴豆基-1H-1,3,2-苯并二氮杂硅杂环戊烷
• 中文别名: （1R，2R）-（-）-[N，N”-双（4-溴苄基）-1,2-环己烷二氨基][（2E）-2-丁烯-1-基]氯硅烷
• 英文名称: (R,R)-trans EZ-CrotylMix
• 英文别名: (R,R)-1,3-Bis(4-bromobenzyl)-2-chlorooctahydro-2-(2E)-crotyl-1H-1,3,2-benzodiazasilole；(3aR,7aR)-1,3-bis[(4-bromophenyl)methyl]-2-[(E)-but-2-enyl]-2-chloro-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazasilole
• CAS: 804559-39-5
• 化学式: C₂₄H₂₉Br₂ClN₂Si
• 分子量: 568.854
• InChiKey: ZRWSDIWSVXXBNG-SESFFYHBSA-N

物化性质

• 熔点：
  92-96°C
• 比旋光度：
  -44.4° (c 1.1, CH2Cl2)
• 沸点：
  573.9±60.0 °C(Predicted)
• 密度：
  1.46±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.59
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-styryloxirane 、 (R,R)-1,3-二(4-溴苄基)-2-氯八氢-2-(2E)-巴豆基-1H-1,3,2-苯并二氮杂硅杂环戊烷 在 scandium tris(trifluoromethanesulfonate) 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以51%的产率得到(1E,4R,5S)-5-methyl-1-phenylhepta-1,6-dien-4-ol
  参考文献：
  名称：

  Enantioselective Allylation and Crotylation of in situ Generated β,γ-Unsaturated Aldehydes

  摘要：

  用催化量的 Sc(OTf)3 处理 2-乙烯基环氧乙烷原位生成的 β,γ-不饱和醛被环应变烯丙基和巴豆基硅烷试剂有效捕获，以高对映体过量的形式提供双烯丙基醇作为单一非对映体。

  DOI：

  10.1055/s-0031-1289565
• 作为产物：
  描述：

  2-丁烯-1-基(三氯)硅烷 、 (R,R)-N,N'-bis(4-bromobenzyl)cyclohexane-1,2-diamine 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 以69%的产率得到(R,R)-1,3-二(4-溴苄基)-2-氯八氢-2-(2E)-巴豆基-1H-1,3,2-苯并二氮杂硅杂环戊烷
  参考文献：
  名称：

  Highly Diastereo- and Enantioselective Reagents for Aldehyde Crotylation

  摘要：

  Two new, crystalline solid, storable, and highly enantioselective reagents for aldehyde crotylation have been developed. Both (cis and trans) crotylsilane reagents are easily prepared in bulk, require trivial reaction conditions, and provide the homoallylic alcohol products with near diastereo- and enantiospecificity in many cases.

  DOI：

  10.1021/ol0480731

文献信息

• A Highly Stereoselective, Efficient, and Scalable Synthesis of the C(1)–C(9) Fragment of the Epothilones
  作者：Corinne N. Foley、James L. Leighton

  DOI：10.1021/acs.orglett.5b03034

  日期：2015.12.4

  second-generation synthesis of the C(1)–C(9) fragment of the epothilones is reported. The key tandem intramolecular silylformylation/crotylsilylation/“aprotic” Tamao oxidation sequence has been redeveloped as a stepwise intermolecular variant, allowing excellent levels of diastereoselectivity in the crotylation step and proceeds in 50% overall yield on gram scale. An improved synthesis of the homopropargyl

  报道了埃博霉素的C（1）–C（9）片段的第二代合成。关键的串联分子内甲硅烷基甲酰化/巴豆基甲硅烷基化/“非质子” Tamoo氧化顺序已被重新开发为逐步的分子间变体，从而在巴甲酰化步骤中具有极佳的非对映选择性，并以克级计获得了50％的总收率。还描述了高炔丙醇起始原料的改进的合成，其从廉价的起始原料开始以四个步骤进行，并且ee＞ 99％，并且适合于多克规模。
• COMPOSITIONS AND METHODS FOR STEREOSELECTIVE ALDEHYDE ALLYLATION AND CROTYLATION
  申请人：KIM Hyunwoo

  公开号：US20120190875A1

  公开（公告）日：2012-07-26

  Compositions and methods for practical, stereoselective allylation and crotylation for aldehyde substrates are described. The compositions and methods comprise reagents for allylation and/or crotylation and acids. In some embodiments, the reagents and acids are pre-mixed.

  本发明描述了一种用于醛底物的实用、立体选择性的烯丙基化和丙烯基化的组合物和方法。该组合物和方法包括用于烯丙基化和/或丙烯基化的试剂和酸。在一些实施例中，试剂和酸是预混合的。
• Synthesis and Evaluation of a Linkable Functional Group-Equipped Analogue of the Epothilones
  作者：Corinne N. Foley、Liang-An Chen、Dan L. Sackett、James L. Leighton

  DOI：10.1021/acsmedchemlett.7b00131

  日期：2017.7.13

  family of microtubule-stabilizing agents is reported. An analogue of epothilone B in which the C(6) methyl group has been replaced with a 4-azidobutyl group has been prepared by total chemical synthesis, and amides derived from the azido group have been shown to retain the activity of the parent compound. These results set the stage for an evaluation of the potential of the epothilones to serve as the drug

  报道了一种用于埃博霉素微管稳定剂家族的接头策略的验证方法。通过全化学合成制备了埃坡霉素B的类似物，其中的C（6）甲基已被4-叠氮基丁基取代，并且已证明衍生自叠氮基的酰胺保留了母体化合物的活性。这些结果为评价埃博霉素作为抗体-药物结合物和其他选择性靶向肿瘤细胞的结合物的药物成分的潜力奠定了基础。
• A More Comprehensive and Highly Practical Solution to Enantioselective Aldehyde Crotylation
  作者：Hyunwoo Kim、Stephen Ho、James L. Leighton

  DOI：10.1021/ja200712f

  日期：2011.5.4

  The enantioselective crotylation of aldehydes with 1,2-diaminochlorocrotylsilane reagents is effectively catalyzed by Sc(OTf)(3). The one significant limitation on the utility of these reagents - substrate scope - has thus been addressed. The net result is the most comprehensive and highly practical method for enantioselective aldehyde crotylation yet advanced.
• Efficient Asymmetric Synthesis of (+)-SCH 351448
  作者：Sergei Bolshakov、James L. Leighton

  DOI：10.1021/ol0515006

  日期：2005.8.1

  An efficient and stereocontrolled total synthesis of (+)-SCH 351448, a novel activator of low-density lipoprotein receptor promoter, has been achieved with a longest linear sequence of 21 steps. Key steps include applications of the recently developed asymmetric allyl- and crotylsilane reagents and a new protodesilylative version of the tandem silylformylation/allyisilylation reaction, which provides an efficient synthesis of 1,5-syn-diols.