(3S,4R)-3-((1R)-1-<(tert-butyldimethylsilyl)oxy>ethyl)-4-<(1S)-1-(formyl)ethyl>azetidin-2-one | 159496-98-7

• 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-((1R)-1-<(tert-butyldimethylsilyl)oxy>ethyl)-4-<(1S)-1-(formyl)ethyl>azetidin-2-one
• 英文别名: (2R)-2-[(2R,3S)-3-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-4-oxoazetidin-2-yl]propanal
• CAS: 159496-98-7
• 化学式: C₁₄H₂₇NO₃Si
• 分子量: 285.459
• InChiKey: AWGQKELDSOKQGY-IRCOFANPSA-N

物化性质

• 沸点：
  377.4±7.0 °C(Predicted)
• 密度：
  0.985±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.35
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,4R)-3-((1R)-1-<(tert-butyldimethylsilyl)oxy>ethyl)-4-<(1S)-1-(formyl)ethyl>azetidin-2-one 在 二异丁基氢化铝 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.5h， 生成 (3S,4R)-3-((1R)-1-<(tert-butyldimethylsilyl)oxy>ethyl)-4-<(1S,2E)-(4-benzoyloxy-1-methyl)-2-butenyl>-1-azetidin-2-one
  参考文献：
  名称：

  π-烯丙基钯配合物环化合成1β-甲基碳青霉烯类抗生素前体

  摘要：

  从市售的 4-乙酰氧基氮杂环丁烷-2-one 4 开始，开发了双环 1β-甲基碳青霉烯类抗生素前体的高效非对映选择性多步合成。手性钌催化剂用于氢化步骤以控制 1 处的 β-立体化学-位置，并且使用π-烯丙基钯闭环策略形成功能化碳青霉烯骨架。

  DOI：

  10.1002/(sici)1099-0690(199903)1999:3<621::aid-ejoc621>3.0.co;2-a
• 作为产物：
  描述：

  (3S,4R)-3-<(R)-1-tert-Butyldimethylsilyloxyethyl>-4-<(S)-1-methylallyl>-2-azetidinone 在 二甲基硫 、 臭氧 作用下， 生成 (3S,4R)-3-((1R)-1-<(tert-butyldimethylsilyl)oxy>ethyl)-4-<(1S)-1-(formyl)ethyl>azetidin-2-one
  参考文献：
  名称：

  Efficient and practical synthesis of 1⊝methylcarbapenems

  摘要：

  An efficient and practical method of synthesizing 1 beta-methylcarbapenem, S-4661, was developed. (4R)-4-[(1S)-1-Methylallyl]-2-azetidinone, 2, prepared stereoselectively from commercially available acetoxy-azetidinone 3, was converted to the beta-keto ester 6 in four steps. The iodonium ylide 5 was prepared from 6, then cyclized to obtain the bicyclic beta-keto ester 4. Finally, 4 was processed to the target product, S-4661, by conventional procedures. (C) 1997, Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(96)01093-9

文献信息

• A highly refined version of the α-keto ester based carbapenem synthesis: The total synthesis of meropenem
  作者：Amar S. Prashad、Nancy Vlahos、Paul Fabio、Gregg B. Feigelson

  DOI：10.1016/s0040-4039(98)01523-8

  日期：1998.9

  The α-keto ester based carbapenem synthesis has been refined so that all deprotections and the ring forming cyclization can be carried out in a single step.

  基于α-酮酯的碳青霉烯合成方法已经过完善，因此所有脱保护和成环环化反应都可以在一个步骤中完成。
• WO2006/82054
  申请人：——

  公开号：——

  公开（公告）日：——
• Regio- and Stereoselective Synthesis of Key 1-Methyl Carbapenem Intermediates via Hydroformylation Using a Zwitterionic Rhodium Catalyst
  作者：H. S. Park、E. Alberico、H. Alper

  DOI：10.1021/ja993080j

  日期：1999.12.1

  The asymmetric hydroformylation of a 4-vinyl beta-lactam catalyzed by a rhodium catalyst with a chiral phosphine ligand was investigated. The catalytic system consisting of a zwitterionic rhodium catalyst, (NBD)Rh+(C6H5B-Ph3) 4, and (S,S)-2,4 bis(diphenylphosphino)pentane, (S,S)-BDPP, gave branched aldehydes in high regio- and stereoselectivity. The hydroformylated products are key intermediates in the synthesis of 1-methylcarbapenem antibiotics. Using (3S,4R)-3-[(R)-1-(tert-butyldimethyl-silyloxy)ethyl]-4-vinyl-2-azetidinone (5a) as the reactant afforded aldehydes in a 97:3 branched-to-linear ratio and 91:9 to beta- to alpha-branched isomers. The regio (branched/linear)- and stereoselectivity (beta/alpha) was >99:1 when (3S,4R)-1-N-BOC-3-[(R)-1-methoxyerhyl]-4-vinyl-2-azetidinone was used as the substrate (5q).
• Stereoselective synthesis of 1-methylcarbapenem precursors: studies on the diastereoselective hydroformylation of 4-vinyl β-lactam with aminophosphonite–phosphinite and aminophosphine–phosphite rhodium(I) complexes
  作者：Edoardo Cesarotti、Isabella Rimoldi

  DOI：10.1016/j.tetasy.2004.10.021

  日期：2004.12

  The asymmetric hydroformylation of variously N-substituted 4-vinyl beta-lactams catalyzed by rhodium aminophosphonite- phosphinite and rhodium aminophosphine-phosphite complexes was studied. These products are valuable intermediates in the preparation of 1-methylcarbapenem antibiotics; the stereo selectivity to the desired beta-isomer is related to the presence of a substituent at the N atom of the beta-lactain ring. The regioselectivity (branched/linear) but not the stereoselectivity ( beta/alpha) was found to be dependent on the substrate to catalyst ratio. (C) 2004 Published by Elsevier Ltd.
• A New Stereocontrolled Approach to 1β-Methylcarbapenem:  Asymmetric Hydroformylation of 4-Vinyl β-Lactams Catalyzed by Rh(I) Complexes of Chiral Phosphine−Phosphites and Phosphine−Phosphinites
  作者：Kyoko Nozaki、Wen-ge Li、Toshihide Horiuchi、Hidemasa Takaya、Takao Saito、Akifumi Yoshida、Kazuhiko Matsumura、Yasushi Kato、Takashi Imai、Takashi Miura、Hidenori Kumobayashi

  DOI：10.1021/jo961689m

  日期：1996.1.1