N-benzyloxycarbonyl-cis-2(R)-(acetoxymethyl)-6(S)-(hydroxymethyl)piperidine | 144433-72-7

• 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: N-benzyloxycarbonyl-cis-2(R)-(acetoxymethyl)-6(S)-(hydroxymethyl)piperidine
• 英文别名: (2R,6S)-2-acetyloxymethyl-1-benzyloxycarbonyl-6-hydroxymethylpiperidine；N-benzyloxycarbonyl-cis-2(R)-acetoxymethyl-6(S)-hydroxymethylpiperidine；N-carbobenzoxy-cis-2(R)-(acetoxymethyl)-6(S)-(hydroxymethyl)piperidine；benzyl (2R,6S)-2-(acetyloxymethyl)-6-(hydroxymethyl)piperidine-1-carboxylate
• CAS: 144433-72-7
• 化学式: C₁₇H₂₃NO₅
• 分子量: 321.373
• InChiKey: BCBKYCKCENNWQG-JKSUJKDBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  76.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-benzyloxycarbonyl-cis-2(R)-(acetoxymethyl)-6(S)-(hydroxymethyl)piperidine 在 potassium permanganate 、 硫酸 、 palladium 10% on activated carbon 、 氢气 、 甲基三辛基氯化铵 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙酸乙酯 、 甲苯 为溶剂， 反应 75.5h， 生成 cis-(2S,6R)-6-hydroxymethyl-2-(1-hydroxy-1,1-diphenylmethyl)piperidine
  参考文献：
  名称：

  cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes as catalysts for oxidative alkenol cyclization by tert-butyl hydroperoxide

  摘要：

  cis-2,6-Bis-(methanolate)-piperidine oxovanadium(V) complexes are Lewis acids able to catalyze oxidative cyclization of alkenols by tert-butyl hydroperoxide (TBHP). Terminal dimethyl-substituted (prenyl-type) 4-pentenols bearing an alkyl or a phenyl group in position 1 afford under such conditions 2,5-cis-derivatives of 2-(tetrahydrofuran-2-yl)-2-propanol as major and tetrahydropyran-3-ols as minor products (four examples). Oxidizing 1-phenyl-6-methylhept-5-en-l-ol yields a 75125-mixture of the derived 2-(tetrahydropyran-2-yl)-2-propanol and an oxepan-3-ol, whereas 2-propenols give epoxides in up to 94% yield. Epoxidizing geraniol by TBHP in the presence of a vanadium catalyst prepared from (2,5,6R)-2-diphenylmethanol-6-hydroxymethylpiperidine occurs enantioselectively. Highfield shifts of vanadium-51 resonances upon adding alkyl hydroperoxides to solutions of cis-2,6-bis-(methanolate)-piperidine vanadium(V) complexes point to vanadium(V) tert-butyl peroxy complex formation as key step for activating peroxides. (C) 2014 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2014.02.007
• 作为产物：
  描述：

  N-carbobenzoxy-cis-2,6-bis(hydroxymethyl)piperidine 在 吡啶 、 4-二甲氨基吡啶 、 sodium hydroxide 、 potassium dihydrogenphosphate 作用下， 以 水 、 乙腈 为溶剂， 反应 108.5h， 生成 N-benzyloxycarbonyl-cis-2(R)-(acetoxymethyl)-6(S)-(hydroxymethyl)piperidine
  参考文献：
  名称：

  Enzymatic Route to Chiral, Nonracemic cis-2,6- and cis,cis-2,4,6-Substituted Piperidines. Synthesis of (+)-Dihydropinidine and Dendrobate Alkaloid (+)-241D

  摘要：

  Piperidine-based compounds are an important class of natural alkaloids found in plants, insects, and amphibians. A general asymmetric synthesis of 2-alkyl-6-methylpiperidines is presented via the enzymatic desymmetrization of meso cis-2,6- and cis,cis-2,4,6-substituted piperidines with Aspergillus niger lipase(ANL). The enzymatic reaction proceeds in excellent chemical yield and high enantiotopic selectivity (ee greater than or equal to 98%). The general method is used to effect the synthesis of (+)-dihydropinidine-HCl as well as the first asymmetric synthesis of dendrobate alkaloid (+)-241D.

  DOI：

  10.1021/jo9519569

文献信息

• Chemoenzymatic Synthesis of Both Enantiomers of <i>cis</i>-6-(Hydroxymethyl)- and <i>cis,cis</i>-4-Hydroxy-6-(hydroxymethyl)pipecolic Acids
  作者：Robert Chênevert、Marie-Pascale Morin

  DOI：10.1021/jo9823036

  日期：1999.4.1

  Both enantiomers of cis-6-(hydroxymethyl)- and cis,cis-4-hydroxy-6-(hydroxymethyl)pipecolic acids, piperidine-based nonproteinogenic amino acids, have been synthesized from starting materials obtained from enzymatic desymmetrizations.

  顺式6-（羟甲基）-和顺式-顺式-4-羟基-6-（羟甲基）哌酸的对映异构体都是基于哌啶的非蛋白原性氨基酸，是从酶解对称法获得的起始原料合成的。
• Chemoenzymatic Enantioselective Synthesis of (-)-Indolizidine 167B
  作者：Robert Chênevert、Ghodsi Mohammadi Ziarani、Mohammed Dasser

  DOI：10.3987/com-98-8421

  日期：——

  (5R, 9R)-(-)-Indolizidine 167 B was synthesized in 8 steps from N-benzyloxycarbonyl-cis-2(R)-acetoxymethyl-6(S)-hydroxymethylpiperidine (2) in an overall yield of 60%. This starting material was obtained from enzymatic desymmetrization of the corresponding meso diacetate (1).

  (5R,9R)-(-)-Indolizidine 167 B 是通过 8 步反应从 N-苄氧基羰基-cis-2(R)-乙酰甲基-6(S)-羟甲基哌啶 (2) 合成的，总产率为 60%。该起始材料来源于相应间二乙酸酯 (1) 的酶促不对称拆分。
• Enzyme-catalysed hydrolysis of N-benzyloxycarbonyl-cis-2,6-(acetoxymethyl)piperidine. A facile route to optically active piperidines
  作者：Robert Chênevert、Michael Dickman

  DOI：10.1016/s0957-4166(00)86034-6

  日期：1992.8

  We report the first enzymatic asymmetrization of a piperidine system. Hydrolysis of N-benzyloxycarbonyl-cis-2,6-(acetoxymethyl)piperidine in the presence of Aspergillus niger lipase gave the corresponding 2R, 6S mono-acetate in good chemical yield and very high optical purity (ee greater-than-or-equal-to 98%).
• Chemoenzymatic synthesis of both enantiomers of cis-6-hydroxymethylpipecolic acid
  作者：Robert Chênevert、Marie-Pascale Morin

  DOI：10.1016/0957-4166(96)00260-1

  日期：1996.8

  Both enantiomers of cis-6-hydroxymethylpipecolic acid. a piperidine-based non-proteinogenic amino acid, have been synthesized in high enantiopurity (ee greater than or equal to 98%) via an enzymatic desymmetrization procedure. Copyright (C) 1996 Elsevier Science Ltd
• Enzymatic desymmetrization of meso cis-2,6- and cis,cis-2,4,6-substituted piperidines. Chemoenzymatic synthesis of (5S,9S)-(+)-indolizidine 209D
  作者：Robert Chênevert、Ghodsi Mohammadi Ziarani、Marie Pascale Morin、Mohammed Dasser

  DOI：10.1016/s0957-4166(99)00315-8

  日期：1999.8

  The stereoselective acylation of meso piperidines 3a,b by vinyl acetate (solvent and acyl donor) in the presence of Candida antarctica lipase gave the corresponding (2S,6R) and (2S,4R,6R) monoesters 2a,b in high enantiomeric purity. (5S,9S)-(+)-Indolizidine 209D was prepared in eight steps from (2S,6R)-2a. (C) 1999 Elsevier Science Ltd. All rights reserved.