6-[(tert-Butyldimethylsilyl)oxy]cyclodecanone tosylhydrazone | 152063-74-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 6-[(tert-Butyldimethylsilyl)oxy]cyclodecanone tosylhydrazone
• 英文别名: N-[[6-[tert-butyl(dimethyl)silyl]oxycyclodecylidene]amino]-4-methylbenzenesulfonamide
• CAS: 152063-74-6
• 化学式: C₂₃H₄₀N₂O₃SSi
• 分子量: 452.734
• InChiKey: LROCQVVOXGVIOW-UHFFFAOYSA-N

物化性质

• 沸点：
  524.0±60.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.15
• 重原子数：
  30.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  67.76
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  6-[(tert-Butyldimethylsilyl)oxy]cyclodecanone tosylhydrazone 在 正丁基锂 、 molecular sieve 、 四甲基乙二胺 、 四丁基氟化铵 、 sodium acetate 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 49.25h， 生成 (Z)-5-Cyclodecenone
  参考文献：
  名称：

  Electrophilic and radical transannular cyclizations of 5-cyclodecenone to give either hydronaphthalene or hydroazulene products

  摘要：

  The transannular cyclizations of the E and Z double-bond isomers of 5-cyclodecenone were investigated in order to determine the regio- and stereochemical preferences of the unsubstituted ring system. Electrophilic cyclization of the E isomer under either protic or Lewis acid conditions led to hydronaphthalenols with a preference for the trans ring fusion, while the Z led to only cis-fused hydronaphthalenols. Cyclization of the ketyl radical generated from the ketone led exclusively to a cis-fused hydroazulenol, regardless of double-bond geometry, although the E isomer was considerably more reactive than the Z isomer. The stereochemistry of the ring fusion in the products from (E)-5-cyclodecenone can be rationalized by cyclization through its lowest energy conformations in which the carbonyl oxygen is anti to the alkene hydrogen at C6, leading to the trans-fused hydronaphthalenol, and syn to the alkene hydrogen at C5, leading to the cis-fused hydroazulenol. For (Z)-5-cyclodecenone, molecular mechanics calculations found two low energy conformations, only one of which brings the alkene and the carbonyl groups close enough for their reaction with each other. In this conformation, the alkene hydrogens at C5 and C6 are syn to the oxygen of the ketone, leading to a cis ring fusion regardless of whether 1,5- or 1,6-cyclization is observed. The difference in regiochemistry in radical versus electrophilic cyclizations is explicable on the basis of the differences in mechanism for the two reaction pathways. The radical cyclizations are kinetic in nature with the ketyl radical adding to the proximate C5 alkene carbon in a very exothermic step, akin to the cyclization of 1-hexenyl radicals. The stereochemistry of the acid-induced cyclizations can be explained through the intermedicacy of either nonclassical or contact ion pairs, the regiochemistry reflecting the greater stability of the hydronaphthalene ring system over the hydroazulene. A system of nomenclature for unambiguously labeling each of the low energy conformations of (E)-5-cyclodecenones is also proposed.

  DOI：

  10.1021/jo00075a025
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 6-[(tert-Butyldimethylsilyl)oxy]cyclodecanone tosylhydrazone
  参考文献：
  名称：

  Electrophilic and radical transannular cyclizations of 5-cyclodecenone to give either hydronaphthalene or hydroazulene products

  摘要：

  The transannular cyclizations of the E and Z double-bond isomers of 5-cyclodecenone were investigated in order to determine the regio- and stereochemical preferences of the unsubstituted ring system. Electrophilic cyclization of the E isomer under either protic or Lewis acid conditions led to hydronaphthalenols with a preference for the trans ring fusion, while the Z led to only cis-fused hydronaphthalenols. Cyclization of the ketyl radical generated from the ketone led exclusively to a cis-fused hydroazulenol, regardless of double-bond geometry, although the E isomer was considerably more reactive than the Z isomer. The stereochemistry of the ring fusion in the products from (E)-5-cyclodecenone can be rationalized by cyclization through its lowest energy conformations in which the carbonyl oxygen is anti to the alkene hydrogen at C6, leading to the trans-fused hydronaphthalenol, and syn to the alkene hydrogen at C5, leading to the cis-fused hydroazulenol. For (Z)-5-cyclodecenone, molecular mechanics calculations found two low energy conformations, only one of which brings the alkene and the carbonyl groups close enough for their reaction with each other. In this conformation, the alkene hydrogens at C5 and C6 are syn to the oxygen of the ketone, leading to a cis ring fusion regardless of whether 1,5- or 1,6-cyclization is observed. The difference in regiochemistry in radical versus electrophilic cyclizations is explicable on the basis of the differences in mechanism for the two reaction pathways. The radical cyclizations are kinetic in nature with the ketyl radical adding to the proximate C5 alkene carbon in a very exothermic step, akin to the cyclization of 1-hexenyl radicals. The stereochemistry of the acid-induced cyclizations can be explained through the intermedicacy of either nonclassical or contact ion pairs, the regiochemistry reflecting the greater stability of the hydronaphthalene ring system over the hydroazulene. A system of nomenclature for unambiguously labeling each of the low energy conformations of (E)-5-cyclodecenones is also proposed.

  DOI：

  10.1021/jo00075a025

文献信息

• Synthesis of a cis-5-cyclodecenone and cis fused hydronaphthalenols through control of the stereochemistry of the oxy-Cope rearrangement with the tri-n-propylsilyl substituent
  作者：Yongliang Chu、David Colclough、David Hotchkin、Myla Tuazon、James B. White

  DOI：10.1016/s0040-4020(97)00952-6

  日期：1997.10

  In the course of preparing a trimethylsilyl substituted 5-cyclodecenone through anionic oxy-Cope rearrangement of a trans-1,2-divinylcyclohexanol, it was discovered that the silyl substituent in the divinylcyclohexanol is positioned so that it destabilizes [3,3]-sigmatropic rearrangement through the normally observed chair-like transition state. In the case of the tri-n-propylsilyl derivative, oxy-Cope

  在通过反式-1,2-二乙烯基环己醇的阴离子氧基-Cope重排制备三甲基甲硅烷基取代的5-环癸烯酮的过程中，发现二乙烯基环己醇中的甲硅烷基取代基的位置使得其使[3,3]-σ不稳定通过通常观察到的椅子状过渡状态进行重新排列。在三的情况下Ñ -propylsilyl衍生物，氧- Cope重排，观察到通过舟状过渡状态，以发生只得到（ë）-5-（三- Ñ -propylsilyl）-5- cyclodecenone与相对于环的顺式双键。酸诱导的跨环环Ë 异构体导致1，6-环化并生成顺式融合萘二酚。