(3S,4R)-3-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-4-[(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-azetidin-2-one | 114463-14-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: (3S,4R)-3-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-4-[(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-azetidin-2-one
• 英文别名: (3S,4R)-3-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-4-[(2R)-1-[tert-butyl(dimethyl)silyl]oxypropan-2-yl]azetidin-2-one
• CAS: 114463-14-8
• 化学式: C₂₀H₄₃NO₃Si₂
• 分子量: 401.737
• InChiKey: AVTUKWQILIVYNA-YLFCFFPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.17
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,4R)-3-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-4-[(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-azetidin-2-one 在 盐酸 作用下， 以 甲醇 、 水 为溶剂， 反应 48.0h， 以80%的产率得到(3S,4R)-3-<(R)-1-(t-butyldimethylsilyloxy)ethyl>-4-<(R)-1-(hydroxymethyl)ethyl>-2-azetidinone
  参考文献：
  名称：

  1β-甲基碳青霉烯关键中间体的硝酮环加成途径

  摘要：

  1β-甲基碳青霉烯关键中间体，(3S,4S)-3-[(R)-1-(叔丁基二甲基甲硅烷氧基)乙基]-4-[(R)-1-羧乙基]-2-氮杂环丁酮，由（ S)-3-羟基-2-甲基丙酸甲酯通过手性硝酮与巴豆酸苄酯的1,3-偶极环加成反应作为关键反应。

  DOI：

  10.1246/bcsj.60.3337
• 作为产物：
  描述：

  (2S,3R,4R)-tert-Butyl 3--5-((tert-butyldimethylsilyl)oxy)-2-((R)-1-hydroxyethyl)-4-methylpentanoate 在 palladium dihydroxide 咪唑 、 乙基溴化镁 、 氢气 作用下， 以 四氢呋喃 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 146.0h， 生成 (3S,4R)-3-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-4-[(R)-2-(tert-butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-azetidin-2-one
  参考文献：
  名称：

  A Three Component Coupling Approach to a Chiral 1.beta.-Methylcarbapenem Key Intermediate

  摘要：

  Conjugate addition of N-benzyl-N((R)-1-phenylethyl)amine (R)-5 to (R)-(E)-tert-butyl 5-((tert-butyldimethylsilyl)oxy)-4-methyl-2-pentenoate (10a) produced the (3S,4R)-syn-adduct 14 with essentially 100% de in 84% yield, whereas the addition of (S)-5 to 10a afforded the (3R,4R)-anti-adduct 15 with essentially 100% de in 95% yield. The syn adduct 14 was converted upon sequential treatment with lithium diisopropylamide-methylaluminum dichloride-acetaldehyde to the key intermediate 21; the diastereoisomer ratio of 21 to other diasteroisomers was 80:20. Conversion of 21 to a 1 beta-methylcarbapenem key intermediate 26 was carried out readily according to the known procedures.

  DOI：

  10.1021/jo00106a027

文献信息

• Highly stereocontrolled synthesis of the key intermediate of 1β-methylcarbapenem antibiotic via intramolecular nitrone 1,3-dipolar cycloaddition
  作者：Masataka Ihara、Masanobu Takahashi、Keiichiro Fukumoto、Tetsuji Kametani

  DOI：10.1039/c39880000009

  日期：——

  The key synthetic intermediate of 1β-methylcarbapenem antibiotic, (–)-(3S, 4R)-3-[(1R)-1-t- butyl-dimethylsiloxyethyl]-4-[(2R)-2-(1-hydroxypropyl)]azetidin-2-one (2), was synthesised from (R)-methyl 3-hydroxy-2-methylpropionate with high stereoselectivity via intramolecular nitrone 1,3-dipolar cycloaddition.

  1β-甲基卡巴培南抗生素的关键合成中间体（-）-（3 S，4 R）-3-[（1 R）-1-叔丁基-二甲基甲硅烷氧基乙基] -4-[（2 R）-2-（通过分子内的硝酮1,3-偶极环加成反应，由（R）-3-羟基-2-甲基丙酸甲酯以高的立体选择性合成1-羟丙基）]氮杂环丁烷-2-酮（2）。
• A new diastereoselective synthesis of a 1β-methylcarbapenem intermediate
  作者：Chang-Young Oh、Won-Hun Ham

  DOI：10.1039/a907922j

  日期：——

  A 1β-methylcarbapenem key intermediate is synthesized from methyl (R)-3-hydroxybutyrate via the diastereoselective alkylation and regioselective cuprate ring opening of a chiral epoxide which is readily prepared from Sharpless asymmetric epoxidation of the corresponding allylic alcohol.

  通过手性环氧化物的非对映选择性烷基化和区域选择性杯状开环，从(R)-3-羟基丁酸甲酯合成了 1δ-甲基碳青霉烯关键中间体。
• A Stereoselective Synthesisof a Key Intermediate to 1β-Methylcarbapenem via AziridineRing-opening Reaction
  作者：Sung Ho Kang、Mihyong Kim、Do Hyun Ryu

  DOI：10.1055/s-2003-39910

  日期：——

  A stereocontrolled synthesis of azetidinone 3 as a key intermediate to 1β-methylcarhapenem 2 has been achieved via iodoamidation of trichloroacetimidate prepared from (Z)-olefinic allylic alcohol 6, aziridine ring-openingreaction with cyanide nucleophile and a tandem β-lactam formation.

  氮杂环丁酮 3 作为 1β-甲基碳青霉烯 2 的关键中间体的立体控制合成已通过由 (Z)-烯丙醇 6 制备的三氯乙酰亚胺酯的碘酰胺化、氮丙啶与氰化物亲核试剂的开环反应和串联 β-内酰胺形成实现。
• Highly enantioselective construction of the key azetidin-2-ones for the synthesis of carbapenem antibiotics via intramolecular C–H insertion reactions of α-methoxycarbonyl-α-diazoacetamides catalysed by chiral dirhodium() carboxylates
  作者：Masahiro Anada、Nobuhide Watanabe

  DOI：10.1039/a803176b

  日期：——

  A highly enantioselective construction of 3-oxa-1-azabicyclo[4.2.0]octanes (up to 96% ee) has been achieved by intramolecular C–H insertion of α-methoxycarbonyl-α-diazoacetamides catalysed by dirhodium(II) complexes incorporating N-phthaloyl-(S)-amino acids as chiral bridging ligands, which provides a new, catalytic asymmetric route to key intermediates for carbapenem antibiotics.

  通过分子内 CâH 插入δ-甲氧羰基-δ-重氮乙酰胺，在δ-甲氧羰基-δ-重氮乙酰胺分子内催化下，实现了 3-oxa-1-azabicyclo[4.2.0]辛烷（ee值高达 96%）的分子内 CâH 插入反应，该反应由含有 N-邻苯二甲酰-(S)-氨基酸作为手性桥接配体的二铑(II)配合物催化，为碳青霉烯类抗生素的关键中间体提供了一条新的催化不对称途径。
• Nitrone Cycloaddition Route to the 1β-Methylcarbapenem Key Intermediate
  作者：Yoshio Ito、Yoshikazu Kimura、Shiro Terashima

  DOI：10.1246/bcsj.60.3337

  日期：1987.9

  The 1β-methylcarbapenem key intermediate, (3S,4S)-3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-4-[(R)-1-carboxyethyl]-2-azetidinone, was prepared from (S)-methyl 3-hydroxy-2-methylpropionate by employing 1,3-dipolar cycloaddition of the chiral nitrone with benzyl crotonate as a key reaction.

  1β-甲基碳青霉烯关键中间体，(3S,4S)-3-[(R)-1-(叔丁基二甲基甲硅烷氧基)乙基]-4-[(R)-1-羧乙基]-2-氮杂环丁酮，由（ S)-3-羟基-2-甲基丙酸甲酯通过手性硝酮与巴豆酸苄酯的1,3-偶极环加成反应作为关键反应。