(4S,5S)-4,5-Dimethoxymethyl-2-(N-p-methoxyphenyl)iminomethyl-2-methyl-1,3-dioxolane | 139308-00-2

• 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: (4S,5S)-4,5-Dimethoxymethyl-2-(N-p-methoxyphenyl)iminomethyl-2-methyl-1,3-dioxolane
• CAS: 139308-00-2
• 化学式: C₁₆H₂₃NO₅
• 分子量: 309.362
• InChiKey: IQMLZDKAGIZTEC-CNTTZWEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.19
• 重原子数：
  22.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  58.51
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (4S,5S)-4,5-Dimethoxymethyl-2-(N-p-methoxyphenyl)iminomethyl-2-methyl-1,3-dioxolane 在 二氯乙基铝 、 三溴化硼 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 0.67h， 生成 (R)-2-((4S,5S)-4,5-Bis-hydroxymethyl-2-methyl-[1,3]dioxolan-2-yl)-1-(4-methoxy-phenyl)-2,3-dihydro-1H-pyridin-4-one
  参考文献：
  名称：

  Stereospecific Synthesis of Piperidine Skeleton by [4+2] Cycloaddition, Leading to the Synthesis of Piperidines of Biological Interests

  摘要：

  [4+2] Cycloaddition reaction between a chiral imine possessing an auxiliary derived from tartaric acid and Danishefsky diene was studied, and the reaction promoted by boron trifluoride etherate gave 2,3-dehydropiperidin-4-one in a stereospecific manner. The adduct thus obtained was converted into (S)-coniine derivatives without loss of the stereochemical integrity.

  DOI：

  10.3987/com-99-s47
• 作为产物：
  描述：

  (S,S)-(-)-1,4-二甲氧基-2,3-丁二醇 在 对甲苯磺酸 草酰氯 、 二甲基亚砜 作用下， 生成 (4S,5S)-4,5-Dimethoxymethyl-2-(N-p-methoxyphenyl)iminomethyl-2-methyl-1,3-dioxolane
  参考文献：
  名称：

  通过酯烯酸酯和手性亚胺缩合，立体构筑β-内酰胺骨架

  摘要：

  酯烯醇酸酯与1,3-二氧戊环的手性亚胺的加成反应中的非对面选择性可以由（S，S）-1,4-二甲氧基-2,3-丁二醇作为手性助剂来调节。的金属烯醇化物适当选择使用。加入烯醇锂提供了（4S）-β-内酰胺，而相应的（4R）-β-内酰胺通过烯醇钛与手性亚胺的缩合获得。

  DOI：

  10.1016/0040-4039(91)80535-e

文献信息

• Highly Stereodivergent Approach to Both Enantiomers of 4-Substituted β-Lactams via Diastereofacially Controlled Addition of Enolates of<i>t</i>-Butyl Acetate to a Chiral Imine
  作者：Makoto Shimizu、Yutaka Ukaji、Junko Tanizaki、Tamotsu Fujisawa

  DOI：10.1246/cl.1992.1349

  日期：1992.7

  Addition of lithium or triisopropoxytitanium enolate derived from t-butyl acetate to a chiral imine possessing dioxolane ring as a chiral auxiliary gave (3S)-β-amino ester exclusively, whereas chlorozinc enolate underwent re-facial attack to give (3R)-isomer with good selectivity. The β-amino esters thus obtained were readily converted to the corresponding (4S)- and (4R)-β-lactams respectively without loss of the stereochemical integrity at C-4 of the β-lactam rings.

  将从叔丁基乙酸酯衍生的锂或三异丙氧基钛烯醇盐与具有二氧杂环作为手性辅助基团的手性亚胺反应，得到(3S)-β-氨基酯，而氯锌烯醇盐则发生了再面进攻，选择性较好地生成(3R)-异构体。由此获得的β-氨基酯可以在不损失β-内酯环C-4立体化学完整性的情况下，方便地转化为相应的(4S)-和(4R)-β-内酯。
• Selective synthesis of optically active 3-haloazetidin-2-ones or aziridines by the condensation of various metal enolates of α-haloacetate with a chiral imine
  作者：Tamotsu Fujisawa、Ryuuichirou Hayakawa、Makoto Shimizu

  DOI：10.1016/s0040-4039(00)74774-5

  日期：1992.12

  Reaction products and their diastereofacial selectivity in the condensation of the ester enolates of α-haloacetate with a chiral imine possessing 1,3-dioxolane ring derived from (2S,3S)-1,4-dimethoxy-2,3-butanediol as a chiral auxiliary can be fully controlled by the metal enolate used; i.e., (3R,4R)-3-haloazetidine-2-one is obtained stereoselectively by the use of the triisopropoxytitanium enolates

  α-卤代乙酸酯的烯醇酯与具有由（2 S，3 S）-1,4-二甲氧基-2,3-丁二醇衍生的具有1,3-二氧戊环的手性亚胺缩合的反应产物及其非对映选择性所用的金属烯醇化物可以完全控制手性助剂；即，（3 R，4 R）-3-卤氮杂环丁烷-2-酮是通过使用三异丙氧基钛烯醇盐立体选择性地获得的，而与锂或锌烯醇盐的缩合可提供（2 R，3 S）-或（2 S， 3 R）-氮丙啶。
• Highly Diastereoselective Addition Reaction of Ketene Silyl Acetals to Imines Catalyzed by Samarium(III) Iodide
  作者：Ryuuichirou Hayakawa、Makoto Shimizu

  DOI：10.1246/cl.1999.591

  日期：1999.7

  In the presence of a catalytic amount of a samarium(III) iodide, the addition reaction of ketene silyl acetal to imine afforded the corresponding β-aminoester with high anti-selectivity. The reaction of chiral imine under the same conditions gave β-aminoester with high diastereoselectivity.

  在催化量的碘化钐（III）存在下，乙烯酮甲硅烷基缩醛与亚胺的加成反应得到具有高抗选择性的相应β-氨基酯。手性亚胺在相同条件下反应得到具有高非对映选择性的β-氨基酯。
• A Cation-exchange Resin Promoted Imino Aldol Reaction, Leading to the Synthesis of 2-Isocephem and 2-Oxa-isocephem
  作者：Makoto Shimizu、Masanori Tachi、Iwao Hachiya

  DOI：10.1246/cl.2004.1394

  日期：2004.10

  Imino aldol reaction of ketene silyl acetals with the chiral imine 1 proceeds smoothly to giveβ-amino esters in good yields with high diasetereoselectivity under the influence of a cation-exchange resin, and the subsequent functional group transformations provide a formal synthesis of 2-isocephem and 2-oxa-isocephem β-lactam antibiotics.

  在阳离子交换树脂的作用下，烯酮硅基乙醛与手性亚胺 1 的氨基醛醇反应顺利进行，以良好的收率和较高的二乙醚选择性得到了β-氨基酯，随后的官能团转化提供了 2-isocephem 和 2-oxa-isocephem β-内酰胺抗生素的正式合成。
• Highly Stereocontrolled Construction of 3-Alkoxyazetidin-2-ones Using Ester Enolate-Imine Condensation
  作者：Makoto Shimizu、Takenori Ishida、Tamotsu Fujisawa

  DOI：10.1246/cl.1994.1403

  日期：1994.8

  5-dimethoxymethyl-2-methyl-1,3-dioxolane ring as a chiral auxiliary could be controlled by the enolate metals, the ester parts, and the alkoxy groups. Addition of the titanium enolate provided (3R,4S)-3-alkoxyazetidin-2-one exclusively, while the corresponding (3R,4R)-isomer was obtained predominantly by the condensation using the zinc enolate of t-butyl α-benzyloxy-, phenoxy-, or t-butoxyacetate with the chiral imine

  α-烷氧基乙酸酯的烯醇化物与具有 (4S,5S)-4,5-二甲氧基甲基-2-甲基-1,3-二氧戊环作为手性助剂的手性亚胺的非对映选择性加成反应可以通过烯醇化物金属来控制，酯部分和烷氧基。添加钛烯醇化物仅提供 (3R,4S)-3-alkoxyazetidin-2-one，而相应的 (3R,4R)-异构体主要通过使用叔丁基 α-苄氧基-的烯醇锌缩合获得，苯氧基-或叔丁氧基乙酸酯与手性亚胺。