(tert-butyl)(3-(iodomethyl)but-3-enyl)(dimethyl)silane | 361434-14-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (tert-butyl)(3-(iodomethyl)but-3-enyl)(dimethyl)silane
• 英文别名: tert-butyl(3-(iodomethyl)but-3-enyloxy)dimethylsilane；2-[2-(tert-butyldimethylsiloxy)ethyl]allyl iodide；Tert-butyl-[3-(iodomethyl)but-3-enoxy]-dimethylsilane
• CAS: 361434-14-2
• 化学式: C₁₁H₂₃IOSi
• 分子量: 326.293
• InChiKey: RQABGPAXFIJBOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.39
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (tert-butyl)(3-(iodomethyl)but-3-enyl)(dimethyl)silane 在 Crabtree catalyst 、 dichlorobis(tricyclohexylphosphine)(benzylidene)rhodium 氢气 、 红铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 68.0h， 生成 (5R,7R)-7-[2-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-spiro[4.4]non-3-en-2-one
  参考文献：
  名称：

  An Asymmetric Approach to Spirocylic Systems:  A Formal Synthesis of Zizaene

  摘要：

  A general route to enantiopure spirocarbocycles is described. The use of various chiral bicyclic lactams 1 that have been doubly alkylated with olefinic halides gives good yields of alpha,alpha -disubstituted chiral lactams 2 which were cyclized to spiro-olefins using ring closure metathesis methodology (Grubbs' catalyst). These spirolactams 3, formed in generally excellent yields, were shown to be smoothly transformed into spirocyclopentenone 6, spirocyclohexenone, 7, and spirolactams 8. Further demonstration of this spirocyclization methodology was featured in a formal synthesis of zizaene, by preparing in enantiomeric form the Coates' intermediate 21. This synthetic effort provided additional examples of the synthetic versatility of chiral bicyclic lactams 2a,b.

  DOI：

  10.1021/jo010439p
• 作为产物：
  描述：

  4-(tert-butyldimethylsilyloxy)-2-methylenebutan-1-ol 在 potassium carbonate 、 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 24.0h， 生成 (tert-butyl)(3-(iodomethyl)but-3-enyl)(dimethyl)silane
  参考文献：
  名称：

  An Asymmetric Approach to Spirocylic Systems:  A Formal Synthesis of Zizaene

  摘要：

  A general route to enantiopure spirocarbocycles is described. The use of various chiral bicyclic lactams 1 that have been doubly alkylated with olefinic halides gives good yields of alpha,alpha -disubstituted chiral lactams 2 which were cyclized to spiro-olefins using ring closure metathesis methodology (Grubbs' catalyst). These spirolactams 3, formed in generally excellent yields, were shown to be smoothly transformed into spirocyclopentenone 6, spirocyclohexenone, 7, and spirolactams 8. Further demonstration of this spirocyclization methodology was featured in a formal synthesis of zizaene, by preparing in enantiomeric form the Coates' intermediate 21. This synthetic effort provided additional examples of the synthetic versatility of chiral bicyclic lactams 2a,b.

  DOI：

  10.1021/jo010439p

文献信息

• Stereoselective synthesis of an advanced seco ester intermediate as a precursor toward the synthesis of amphidinolides T1, T3, and T4
  作者：Pradip K. Sasmal、Chandrasekhar Abbineni、Javed Iqbal、K. Mukkanti

  DOI：10.1016/j.tet.2010.05.012

  日期：2010.7

  An efficient, convergent, and stereoselective synthesis of a very advanced intermediate toward the total synthesis of amphidinolides T1, T3, and T4 utilising Evan’s aldol and alkylation reactions, oxy-Michael, cross metathesis, stereoselective Grignard addition, and Yamaguchi esterification reactions as key steps is described.

  高效，收敛和立体选择性合成非常先进的中间体，可利用埃文的羟醛和烷基化反应，氧基-迈克尔基，交叉易位，立体选择性格氏试剂加成和山口酯化反应作为主要步骤，完成两性化合物T1，T3和T4的全合成描述。
• Toward the Total Synthesis of FR901483:  Concise Synthesis of the Azatricyclic Skeleton
  作者：Suvi T. M. Simila、Stephen F. Martin

  DOI：10.1021/jo070732a

  日期：2007.7.1

  that could be transformed into (−)-FR901483 first required the development of a new protecting group, the 1-ethylallyloxycarbamate group, for amines that may be removed under mild conditions. However, because the stereoselectivity in a key step in which a functionalized allyl zinc reagent was added to an intermediate hydroxy-substituted imine was low, this route to (−)-FR901483 is no longer being pursued

  FR901483的氮杂三环核的简明合成已使用一种新颖的策略完成，该策略涉及将亲核性加成至N-酰基亚胺离子，闭环易位，非对映选择性硼氢化和内酯-内酰胺重排，在初步模型研究。将该方法扩展到可以转化为（-）-FR901483的功能更高的中间体的合成中，首先需要开发新的保护基团1-乙基烯丙氧基氨基甲酸酯基团，以便在温和条件下可以除去胺。但是，由于在将官能化的烯丙基锌试剂添加至中间体羟基取代的亚胺中的关键步骤中的立体选择性低，因此不再寻求这种通往（-）-FR901483的途径。
• Enantioselective Copper-Catalyzed Intramolecular O−H Insertion: An Efficient Approach to Chiral 2-Carboxy Cyclic Ethers
  作者：Shou-Fei Zhu、Xiao-Guang Song、Yu Li、Yan Cai、Qi-Lin Zhou

  DOI：10.1021/ja1078464

  日期：2010.11.24

  A copper-catalyzed asymmetric intramolecular O-H insertion of omega-hydroxy-alpha-diazoesters has been accomplished by using chiral spiro bisoxazoline ligands. This highly enantioselective intramolecular O-H insertion reaction provides an efficient approach to a variety of synthetically important chiral 2-carboxy cyclic ethers with different ring sizes as well as substitution patterns.