methyl 3-tert-butyldimethylsilyloxy-2-methylenehexanoate | 164853-27-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl 3-tert-butyldimethylsilyloxy-2-methylenehexanoate
• 英文别名: Methyl 3-[tert-butyl(dimethyl)silyl]oxy-2-methylidenehexanoate
• CAS: 164853-27-4
• 化学式: C₁₄H₂₈O₃Si
• 分子量: 272.46
• InChiKey: IEGDZXGNSZUBLG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 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：

  methyl 3-tert-butyldimethylsilyloxy-2-methylenehexanoate 在 二异丁基氢化铝 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 syn-3-(Hydroxymethyl)-3-<1'-<(tert-butyldimethylsilyl)oxy>butyl>-1-pyrazoline
  参考文献：
  名称：

  1,3-Dipolar Cycloadditions to Baylis-Hillman Adducts: Rationale for the Observed Diastereoselectivity

  摘要：

  Diazomethane and benzonitrile oxide cycloadditions were performed on Baylis-Hillman adducts derived from methyl acrylate and aldehydes (beta'-alkoxy-alpha,beta-unsaturated esters). The reactions proceed in good chemical yields, and their stereochemical outcome can be explained by the ''inside alkoxy effect'' theory. In the case of diazomethane cycloadditions, however, electrostatic factors play a reduced role in comparison to the corresponding nitrile oxide reactions, while steric effects are of major importance in governing the stereoselectivity. This different behavior of the two 1,3-dipoles finds a rationale in the analysis of the atomic charges as calculated at the RHF/3-21G level of theory for the transition structure of these reactions.

  DOI：

  10.1021/jo00120a009
• 作为产物：
  描述：

  己酸,3-羟基-2-亚甲基-,甲基酯 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 生成 methyl 3-tert-butyldimethylsilyloxy-2-methylenehexanoate
  参考文献：
  名称：

  Baylis-Hillman加合物的顺式立体控制二羟基化†

  摘要：

  Baylis-Hillman加合物1的羟基化表现为高水平的非对映异构控制。讨论了解释这种选择性的机械原理。

  DOI：

  10.1002/recl.19951140418

文献信息

• The Importance of Electrostatic Interactions in the Stereoselective 1,3-Dipolar Cycloadditions of Nitrones to Chiral Allyl Ethers: An Experimental and Force Field Approach
  作者：Rita Annunziata、Maurizio Benaglia、Mauro Cinquini、Franco Cozzi、Laura Raimondi

  DOI：10.1002/(sici)1099-0690(199809)1998:9<1823::aid-ejoc1823>3.0.co;2-h

  日期：1998.9

  The 1,3-dipolar cycloaddition of formaldehyde N-benzylnitrone with β′-alkoxy- and γ-alkoxy-α,β-unsaturated esters was investigated. The stereochemical outcome of these reactions was nicely rationalized on the basis of an interpretation of the inside alkoxy theory emphasizing the electrostatic interactions in the reaction TS. The force field approach previously developed for evaluating the stereoselection

  研究了甲醛N-苄基硝酮与β'-烷氧基-和γ-烷氧基-α,β-不饱和酯的1,3-偶极环加成反应。基于对内部烷氧基理论的解释，这些反应的立体化学结果很好地合理化，强调了反应 TS 中的静电相互作用。先前开发的用于评估氧化腈环加成对手性烯烃的立体选择的力场方法已成功扩展到硝酮反应。
• Diastereoselectivity in heterogeneous catalytic hydrogenation of Baylis–Hillman adducts. Total synthesis of (±)-sitophilate
  作者：Cristiano R Mateus、Melissa P Feltrin、Ana M Costa、Fernando Coelho、Wanda P Almeida

  DOI：10.1016/s0040-4020(01)00647-0

  日期：2001.8

  We describe herein a highly diastereoselective total synthesis of racemic sitophilate, based on the results obtained in a diastereoselective heterogeneous catalytic hydrogenation reaction of a set of Baylis-Hillman adducts originating from aliphatic aldehydes. (C) 2001 Published by Elsevier Science Ltd.