(S)-N-(tert-butoxycarbonyl)-4-methoxycarbonyl-2,2,4-trimethyl-3-oxazolidine | 219567-08-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (S)-N-(tert-butoxycarbonyl)-4-methoxycarbonyl-2,2,4-trimethyl-3-oxazolidine
• 英文别名: methyl (S)-3-tert-butoxycarbonyl-2,2,4-trimethyloxazolidine-4-carboxylate；3-O-tert-butyl 4-O-methyl (4S)-2,2,4-trimethyl-1,3-oxazolidine-3,4-dicarboxylate
• CAS: 219567-08-5
• 化学式: C₁₃H₂₃NO₅
• 分子量: 273.329
• InChiKey: MBENUMDOBURJST-ZDUSSCGKSA-N

物化性质

• 沸点：
  315.8±42.0 °C(Predicted)
• 密度：
  1.082±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  65.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (S)-N-(tert-butoxycarbonyl)-4-methoxycarbonyl-2,2,4-trimethyl-3-oxazolidine 在 scandium tris(trifluoromethanesulfonate) 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 48.0h， 生成 (S)-(2-hydroxy-1-hydroxymethyl-1,2-dimethylpropyl)carbamic acid tert-butyl ester
  参考文献：
  名称：

  Synthesis of enantiopure (αMe)Dip and other α-methylated β-branched amino acid derivatives

  摘要：

  This report describes the synthesis of the two enantiomerically pure a-methylated P-branched phenylalanine derivatives, (S)- and (R)-alpha-methyl-beta,beta-diphenylalanine-(alphaMe)Dip-starting from the chiral building blocks (R)- and (S)-N-Boc-N,O-isopropylidene-alpha-methylserine methyl esters, respectively. The key step involves a double alkylation with a Grignard reagent on an ester group. The use of the same protocol for the preparation of other alpha-methylated beta-branched serine derivatives is also described. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00828-5
• 作为产物：
  描述：

  N-BOC-2-甲基-L-丝氨酸 在 对甲苯磺酸 作用下， 以 乙醚 、 苯 为溶剂， 反应 14.5h， 生成 (S)-N-(tert-butoxycarbonyl)-4-methoxycarbonyl-2,2,4-trimethyl-3-oxazolidine
  参考文献：
  名称：

  Synthesis of (S)-N-tert-butoxycarbonyl-N,O-isopropylidene-α-methylserinal: A potential building block for the asymmetric synthesis of non-natural amino acids

  摘要：

  The title compound (S)-alpha-methylserinal acetonide has been efficiently prepared from (S)-alpha-methylserine, which is readily available in enantiomerically pure form by Curtius rearrangement of alpha,alpha-dialkyl 2-cyanoesters obtained by diastereoselective alkylation of (1S,2R,4R)-10-dicyclohexylsulfamoylisobornyl 2-cyanopropanoate using methoxymethyl iodide or paraformaldehyde as electrophiles by an extension of our recently developed methodology for the synthesis of alpha,alpha-dialkylamino acids, (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00937-5

文献信息

• WO2008/16692
  申请人：——

  公开号：——

  公开（公告）日：——
• WO2008/16674
  申请人：——

  公开号：——

  公开（公告）日：——
• Complementary Syntheses of <i>N</i>,<i>O</i>-Protected-(<i>S</i>)-2-methylserine on a Multikilogram Scale
  作者：Michael S. Anson、Hugh F. Clark、Paul Evans、Martin E. Fox、Jonathan P. Graham、Natalie N. Griffiths、Graham Meek、James A. Ramsden、Alastair J. Roberts、Shaun Simmonds、Matthew D. Walker、Matthew Willets

  DOI：10.1021/op100299d

  日期：2011.3.18

  Two complementary and scalable approaches have been used to manufacture multikilogram quantities of N,O-protected-(S)-2-methylserine. The first approach uses a diastereomeric salt resolution of 2-methylserine methyl ester as the (1S)-(+)-camphorsulfonate salt, and was used to rapidly access 15 kg of (S)-3-tert-butoxycarbonyl-2,2,4-trimethyl-1,3-oxazolidine-4-carboxylic acid with > 99% ee. The second approach involves a stereoselective enolate methylation of a chiral cyclic L-serine derivative under cryogenic conditions. The four-step telescoped process, starting from L-serine methyl ester, was used to manufacture 20 kg of (2R,4S)-2-tert-butyl-3-tert-butoxycarbonyl-4-methyl-1,3-oxazolidine-4-carboxylic acid in 52% overall yield and 98% ee. The advantages and disadvantages for scale-up of both approaches are discussed.
• Enantioselective synthesis of (S)- and (R)-α-methylserines: application to the synthesis of (S)- and (R)-N-Boc-N,O-isopropylidene-α-methylserinals
  作者：Alberto Avenoza、Carlos Cativiela、Francisco Corzana、Jesús M. Peregrina、David Sucunza、Marı́a M. Zurbano

  DOI：10.1016/s0957-4166(01)00159-8

  日期：2001.4

  This report describes the synthesis of enantiomerically pure (S)- and (R)-alpha -methylserines on a multigram scale, starting from the Weinreb amide of 2-methyl-2-propenoic acid and using a stereodivergent synthetic route that involves a Sharpless asymmetric dihydroxylation reaction. As a synthetic application of these quaternary alpha -amino acids, they were used as starting materials in the synthesis of the well-known valuable homochiral (S)- and (R)-N-Boc-N,O-isopropylidene-alpha -methylserinal building blocks. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Synthesis of (S)-N-tert-butoxycarbonyl-N,O-isopropylidene-α-methylserinal: A potential building block for the asymmetric synthesis of non-natural amino acids
  作者：Myriam Alías、Carlos Cativiela、María D. Díaz-de-Villegas、JoséA. Gálvez、Yolanda Lapeña

  DOI：10.1016/s0040-4020(98)00937-5

  日期：1998.12

  The title compound (S)-alpha-methylserinal acetonide has been efficiently prepared from (S)-alpha-methylserine, which is readily available in enantiomerically pure form by Curtius rearrangement of alpha,alpha-dialkyl 2-cyanoesters obtained by diastereoselective alkylation of (1S,2R,4R)-10-dicyclohexylsulfamoylisobornyl 2-cyanopropanoate using methoxymethyl iodide or paraformaldehyde as electrophiles by an extension of our recently developed methodology for the synthesis of alpha,alpha-dialkylamino acids, (C) 1998 Elsevier Science Ltd. All rights reserved.