benzyl 2-(dimethoxyphosphoryl)pyrrolidine-1-carboxylate | 347386-37-2

• 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: benzyl 2-(dimethoxyphosphoryl)pyrrolidine-1-carboxylate
• 英文别名: dimethyl N-(benzyloxycarbonyl)pyrrolidine-2-phosphonate；Benzyl 2-dimethoxyphosphorylpyrrolidine-1-carboxylate
• CAS: 347386-37-2
• 化学式: C₁₄H₂₀NO₅P
• 分子量: 313.29
• InChiKey: SWMJRGSXBYMRJG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  benzyl 2-(dimethoxyphosphoryl)pyrrolidine-1-carboxylate 在 palladium 10% on activated carbon 、 Candida antarctica lipase type A, immobilized NZL-101 、 氢气 作用下， 以 乙醇 、 甲基叔丁基醚 为溶剂， 30.0 ℃ 、101.33 kPa 条件下， 反应 90.0h， 生成 (S)-dimethyl N-(benzyloxycarbonyl)pyrrolidine-2-phosphonate
  参考文献：
  名称：

  Enzymatic and chromatographic resolution procedures applied to the synthesis of the phosphoproline enantiomers

  摘要：

  The preparation of enantiomerically pure pyrrolidine-2-phosphonic acid (phosphoproline, Pro(P)) has been addressed through the synthesis of suitable racemates and subsequent resolution by independent enzyme-catalyzed and chiral HPLC methods. First, racemic phosphoproline derivatives bearing the necessary protecting groups have been synthesized in excellent global yields starting from inexpensive materials. Preparative HPLC resolution of the N-Cbz-protected aminophosphonate on a cellulose-based column allowed the isolation of enantiomerically pure enantiomers on a gram scale. Enzyme-catalyzed alkoxycarbonylation of the aminophosphonate was studied using different lipases, solvents, and carbonates. Candida antarctica lipase type A (CAL-A) provided the highest enantioselectivity when combined with benzyl 3-methoxyphenyl carbonate. (c) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.10.016
• 作为产物：
  描述：

  1-(benzyloxycarbonyl)pyrrolidin-2-ol 在 三氟化硼乙醚 、 4-甲基苯磺酸吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 生成 benzyl 2-(dimethoxyphosphoryl)pyrrolidine-1-carboxylate
  参考文献：
  名称：

  Enzymatic and chromatographic resolution procedures applied to the synthesis of the phosphoproline enantiomers

  摘要：

  The preparation of enantiomerically pure pyrrolidine-2-phosphonic acid (phosphoproline, Pro(P)) has been addressed through the synthesis of suitable racemates and subsequent resolution by independent enzyme-catalyzed and chiral HPLC methods. First, racemic phosphoproline derivatives bearing the necessary protecting groups have been synthesized in excellent global yields starting from inexpensive materials. Preparative HPLC resolution of the N-Cbz-protected aminophosphonate on a cellulose-based column allowed the isolation of enantiomerically pure enantiomers on a gram scale. Enzyme-catalyzed alkoxycarbonylation of the aminophosphonate was studied using different lipases, solvents, and carbonates. Candida antarctica lipase type A (CAL-A) provided the highest enantioselectivity when combined with benzyl 3-methoxyphenyl carbonate. (c) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.10.016

文献信息

• Chemical Conversion of Cyclic .ALPHA.-Amino Acids to Cyclic .ALPHA.-Aminophosphonic Acids.
  作者：Mamoru KANAME、Hironori MASHIGE、Shigeyuki YOSHIFUJI

  DOI：10.1248/cpb.49.531

  日期：——

  oxidative decarboxylation of cyclic alpha-amino acids having urethane-type N-protecting groups with lead tetraacetate [Pb(OAc)4] gave 2-hydroxy derivatives, which were transformed into the corresponding alpha-aminophosphonic acid esters by treatment of trialkyl phosphites in the presence of Lewis acids. Deprotection and ester cleavage of the products in the usual manner afforded cyclic alpha-aminophosphonic

  用四乙酸铅[Pb（OAc）4]对具有氨基甲酸酯型N-保护基的环状α-氨基酸进行氧化脱羧，得到2-羟基衍生物，通过处理亚磷酸三烷基酯将其转化为相应的α-氨基膦酸酯。路易斯酸的存在。以常规方式对产物进行脱保护和酯裂解，得到环状α-氨基膦酸。已经实现了将五元和六元环状α-氨基酸方便地化学转化为相应的环状α-氨基膦酸。
• XYZH systems as potential 1,3-dipoles. Part 62: 1,3-Dipolar cycloaddition reactions of metallo-azomethine ylides derived from α-iminophosphonates
  作者：H. Ali Dondas、Yasar Durust、Ronald Grigg、Martin J. Slater、Mohammed Abul Basher Sarker

  DOI：10.1016/j.tet.2005.08.079

  日期：2005.11

  Metallo-azomethine ylides, generated from iminophosphonates in combination with LiBr or AgOAc and bases Et3N, DBU, t-butyl tetramethylguanidine(BTMG) undergo cycloaddition to give dialkyl pyrrolidine-2-phosphonates along with the corresponding Michael adduct in some cases. Cycloadditions with the chiral dipolarophile 5R-(1′R,2′S,5′R-menthyloxy)-2-(5H)-furanone (MOF) afforded enantiopure cycloadducts

  在某些情况下，由亚氨基膦酸酯与LiBr或AgOAc以及碱Et 3 N，DBU，叔丁基四甲基胍（BTMG）结合生成的金属偶氮甲亚胺基化物经过环加成反应，生成吡咯烷-2-膦酸二烷基酯和相应的迈克尔加成物。与手性亲偶极环加成5 - [R - （1' - [R，2'小号，5' - [R -menthyloxy）-2-（5- ħ） -呋喃酮（MOF），得到对映纯的cycloadducts。
• Enzymatic and chromatographic resolution procedures applied to the synthesis of the phosphoproline enantiomers
  作者：Alicia Arizpe、María Rodríguez-Mata、Francisco J. Sayago、María J. Pueyo、Vicente Gotor、Ana I. Jiménez、Vicente Gotor-Fernández、Carlos Cativiela

  DOI：10.1016/j.tetasy.2015.10.016

  日期：2015.12

  The preparation of enantiomerically pure pyrrolidine-2-phosphonic acid (phosphoproline, Pro(P)) has been addressed through the synthesis of suitable racemates and subsequent resolution by independent enzyme-catalyzed and chiral HPLC methods. First, racemic phosphoproline derivatives bearing the necessary protecting groups have been synthesized in excellent global yields starting from inexpensive materials. Preparative HPLC resolution of the N-Cbz-protected aminophosphonate on a cellulose-based column allowed the isolation of enantiomerically pure enantiomers on a gram scale. Enzyme-catalyzed alkoxycarbonylation of the aminophosphonate was studied using different lipases, solvents, and carbonates. Candida antarctica lipase type A (CAL-A) provided the highest enantioselectivity when combined with benzyl 3-methoxyphenyl carbonate. (c) 2015 Elsevier Ltd. All rights reserved.