2-[tert-butyl(dimethyl)silyl]oxy-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]ethanone | 115043-29-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-[tert-butyl(dimethyl)silyl]oxy-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]ethanone
• CAS: 115043-29-3
• 化学式: C₁₃H₂₆O₄Si
• 分子量: 274.433
• InChiKey: SJDVGKCUYQJNKT-NSHDSACASA-N

物化性质

• 沸点：
  291.9±40.0 °C(Predicted)
• 密度：
  0.974±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.73
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-[tert-butyl(dimethyl)silyl]oxy-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]ethanone 在 palladium dihydroxide 氯代二环己基硼烷 、 氢气 、 对甲苯磺酸 、 三乙胺 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 7.5h， 生成
  参考文献：
  名称：

  Double Diastereoselection in Aldol Reactions Mediated by Dicyclohexylchloroborane between l-Erythrulose Derivatives and Chiral Aldehydes. The Felkin−Anh versus Cornforth Dichotomy

  摘要：

  Both matched and mismatched diastereoselections have been observed in aldol reactions of the B,B-dicyclohexylboron enolate of a protected L-erythrulose derivative with a range of chiral aldehydes. The stereochemical outcome of reactions with alpha-methyl aldehydes can be adequately explained within the Felkin-Anh paradigm. In the case of alpha-oxygenated aldehydes, however, strict adherence to this model does not allow for a satisfactory account of the observed results. In such cases, the Cornforth model provides a much better explanation.

  DOI：

  10.1021/jo035159j
• 作为产物：
  描述：

  (2S,3S)-1,2-O-isopropylidene-1,2,3,4-tetrol 在 咪唑 、 重铬酸吡啶 、 3 A molecular sieve 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 36.0h， 生成 2-[tert-butyl(dimethyl)silyl]oxy-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]ethanone
  参考文献：
  名称：

  Marco, Jose L., Journal of Chemical Research, Miniprint, 1988, # 9, p. 2013 - 2016

  摘要：

  DOI：

文献信息

• Aldol Reactions between L-Erythrulose Derivatives and Chiral α-Amino and α-Fluoro Aldehydes: Competition between Felkin-Anh and Cornforth Transition States
  作者：Santiago Díaz-Oltra、Miguel Carda、Juan Murga、Eva Falomir、J. Alberto Marco

  DOI：10.1002/chem.200800956

  日期：2008.10.20

  Both matched and mismatched diastereoselection have been observed in aldol reactions of a boron enolate of a protected L-erythrulose derivative with several chiral alpha-fluoro and alpha-amino aldehydes. Strict adherence to the Felkin-Anh model for the respective transition structures does not account satisfactorily for all the observed results, as previously observed in the case of alpha-oxygenated

  在受保护的L-赤藓糖衍生物的硼烯酸酯与几种手性α-氟和α-氨基醛的醛醇缩合反应中已经观察到匹配的和错配的非对映选择性。如先前在α-氧化醛的情况下所观察到的，对于各个过渡结构严格遵守Felkin-Anh模型并不能令人满意地解决所有观察到的结果。在某些情况下，只有Cornforth模型提供了很好的解释。讨论了影响该二分法的因素，并提出了用于与α-杂原子取代的醛的醛醇缩合反应的通用机理模型。该模型的其他支持是从密度泛函计算中获得的。
• L-(S)-Erythrulose: The synthesis of (R)-1,2,4-butanetriol and of some related C4 chirons.
  作者：E. Van der Eycken、H. De Wilde、L. Deprez、M. Vandewalle

  DOI：10.1016/s0040-4039(00)96619-x

  日期：1987.1

  L-(S)-Erythrulose can easily be transformed into (R)-1,2,4-butanetriol and related C4, chiral building blocks. A formal synthesis of (-)GABOB is presented. Also the formation of 3-methylene-1,2,4-butanetriol derivatives is described.

  L-（S）-赤藓糖可轻松转化为（R）-1,2,4-丁三醇和相关的C 4手性结构单元。提出了（-）GABOB的形式合成。还描述了3-亚甲基-1,2,4-丁三醇衍生物的形成。
• Stereoselective synthesis of anamarine
  作者：Santiago Dı́az-Oltra、Juan Murga、Eva Falomir、Miguel Carda、J.Alberto Marco

  DOI：10.1016/j.tet.2004.02.003

  日期：2004.3

  A stereoselective synthesis of the naturally occurring, α,β-unsaturated lactone anamarine is described. The key step was a highly stereoselective aldol reaction of a protected erythrulose derivative with a chiral aldehyde. Another relevant step was an asymmetric aldehyde allylation with a chiral allylborane. The lactone ring was made by means of a ring-closing metathesis.

  描述了天然存在的α，β-不饱和内酯阿马林的立体选择性合成。关键步骤是受保护的赤藓糖衍生物与手性醛的高度立体选择性醛醇缩合反应。另一个相关步骤是与手性烯丙基硼烷的不对称醛烯丙基化。内酯环通过闭环复分解反应制得。
• Stereoselective Synthesis of (+)-Boronolide
  作者：Miguel Carda、Santiago Rodríguez、Beatriz Segovia、J. Alberto Marco

  DOI：10.1021/jo025813f

  日期：2002.9.1

  The delta-lactone boronolide (+)-1, a pharmacologically active, naturally occurring product, has been synthesized in enantiopure form with L-erythrulose as the chiral starting material. The key steps of the synthesis were a highly stereoselective aldol-reduction one-pot sequence, an indium-mediated diastereoselective aldehyde allylation, and a ring-closing metathesis.

  δ-内酯硼烷内酯（+）-1是一种药理活性的天然产物，已以对映纯形式与L-赤藓糖为手性原料合成。合成的关键步骤是高度立体选择性的醛醇还原一锅序列，铟介导的非对映选择性醛烯丙基化和闭环易位。
• Boron aldol additions with erythrulose derivatives: dependence of stereoselectivity on the type of protecting group
  作者：Miguel Carda、Eva Falomir、Juan Murga、Encarnación Castillo、Florenci González、J. Alberto Marco

  DOI：10.1016/s0040-4039(99)01380-5

  日期：1999.9

  Boron aldol additions of 1-O-silylated 3,4-di-O-benzyl- and 3,4-di-O-benzoyl-l-erythrulose and achiral aldehydes using dicyclohexylboron chloride have been investigated. The dibenzyl derivative gave syn/syn stereoisomers with high stereoselectivity, whereas the dibenzoyl derivative gave syn/anti stereoisomers. It is believed that, while the dibenzoyl erythrulose gives rise to the E enolate in the presence

  已经研究了使用二环己基氯化硼对1 - O-甲硅烷基化的3，4-二-O-苄基-和3，4-二-O-苯甲酰基-1-赤藓糖和非手性醛的硼醇醛加成。二苄基衍生物给出了具有高立体选择性的顺式/顺式立体异构体，而二苯甲酰基衍生物给出了顺式/反式立体异构体。据信，虽然二苯甲酰赤藓酮糖产生了È烯醇化物中的dicyclohexylboron酰氯存在，因为通常与该试剂观察到，只有ž形成在二苄基衍生物的情况下的烯醇化物。