(R)-2-Hydroxy-2-[(S)-1-((R)-4-methyl-oct-2-ynyl)-pyrrolidin-2-yl]-propionic acid methyl ester | 192655-96-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (R)-2-Hydroxy-2-[(S)-1-((R)-4-methyl-oct-2-ynyl)-pyrrolidin-2-yl]-propionic acid methyl ester
• 英文别名: methyl (2R)-2-hydroxy-2-[(2S)-1-[(4R)-4-methyloct-2-ynyl]pyrrolidin-2-yl]propanoate
• CAS: 192655-96-2
• 化学式: C₁₇H₂₉NO₃
• 分子量: 295.422
• InChiKey: XZUQWSVUYPYXAY-HLLBOEOZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-2-Hydroxy-2-[(S)-1-((R)-4-methyl-oct-2-ynyl)-pyrrolidin-2-yl]-propionic acid methyl ester 在 titanium(IV) isopropylate 、 重水 、 异丙基氯化镁 作用下， 生成
  参考文献：
  名称：

  Efficient and Practical Method for Synthesizing N-Heterocyclic Compounds Using Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by Ti(O-i-Pr)₄/2i-PrMgX Reagent. Synthesis of Quinolones, Pyrroles, Indoles, and Optically Active N-Heterocycles Including Allopumiliotoxin Alkaloid 267A

  摘要：

  Treatment of N-(2- or 3-alkynyl)amino esters with a low-valent titanium reagent diisopropoxy(eta(2)-propene)titanium (1), generated in situ by the reaction of Ti(O-i-Pr)(4) and 2i-PrMgCl, resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford alpha-alkylidene-pyrrolidinones or -piperidinones. Thus, treatment of N-propargyl-anthranilates 5, -indole-2-carboxylates 10, or -pyrrole-2-carboxylates 13 with 1 gave 4-quinolones 7, [1,2-a]indoles, or [1,2-a]pyrroles, respectively. Similarly, N-alkynylated alpha- or beta-amino esters 14 or 15 with 1 afforded N-heterocycles 18 or 19. In the reaction of N-(2- or 3-alkenyl)amino esters with 1, the resulting INAS product underwent intramolecular carbonyl addition (ICA) reaction to afford the N-heterocyclic compounds having a cyclopropanol moiety in good to excellent yields. Thus, the treatment of N-alkenyl-anthranilate 4a, -indole-2-carboxylates 8 and 9, or -pyrrole-2-carboxylates 11 and 12 with 1 gave the corresponding quinoline derivative 6a, [1,2-a]indoles, or [1,2-a]pyrroles, respectively. The optically active N-heterocyclic compounds 20 and 21 were obtained from N-alkenylated alpha- or beta-amino esters 16 or 17. A highly efficient total synthesis of allopumiliotoxin alkaloid 267A has also been accomplished. Thus, the N-propargyl-2[(1-hydroxy-1-methoxycarbonyl)ethyl]pyrrolidine 24 (from L-proline in six steps) reacted with 1 to afford the corresponding indolidinone 25 in 67% yield, which has previously been converted to allopumiliotoxin 267A.

  DOI：

  10.1021/ja970810j
• 作为产物：
  描述：

  (S)-1-BOC-2-乙酰基-吡咯烷 在 正丁基锂 、 mercury(II) perchlorate 、 苯甲醚 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 为溶剂， 反应 66.5h， 生成 (R)-2-Hydroxy-2-[(S)-1-((R)-4-methyl-oct-2-ynyl)-pyrrolidin-2-yl]-propionic acid methyl ester
  参考文献：
  名称：

  Efficient and Practical Method for Synthesizing N-Heterocyclic Compounds Using Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by Ti(O-i-Pr)₄/2i-PrMgX Reagent. Synthesis of Quinolones, Pyrroles, Indoles, and Optically Active N-Heterocycles Including Allopumiliotoxin Alkaloid 267A

  摘要：

  Treatment of N-(2- or 3-alkynyl)amino esters with a low-valent titanium reagent diisopropoxy(eta(2)-propene)titanium (1), generated in situ by the reaction of Ti(O-i-Pr)(4) and 2i-PrMgCl, resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford alpha-alkylidene-pyrrolidinones or -piperidinones. Thus, treatment of N-propargyl-anthranilates 5, -indole-2-carboxylates 10, or -pyrrole-2-carboxylates 13 with 1 gave 4-quinolones 7, [1,2-a]indoles, or [1,2-a]pyrroles, respectively. Similarly, N-alkynylated alpha- or beta-amino esters 14 or 15 with 1 afforded N-heterocycles 18 or 19. In the reaction of N-(2- or 3-alkenyl)amino esters with 1, the resulting INAS product underwent intramolecular carbonyl addition (ICA) reaction to afford the N-heterocyclic compounds having a cyclopropanol moiety in good to excellent yields. Thus, the treatment of N-alkenyl-anthranilate 4a, -indole-2-carboxylates 8 and 9, or -pyrrole-2-carboxylates 11 and 12 with 1 gave the corresponding quinoline derivative 6a, [1,2-a]indoles, or [1,2-a]pyrroles, respectively. The optically active N-heterocyclic compounds 20 and 21 were obtained from N-alkenylated alpha- or beta-amino esters 16 or 17. A highly efficient total synthesis of allopumiliotoxin alkaloid 267A has also been accomplished. Thus, the N-propargyl-2[(1-hydroxy-1-methoxycarbonyl)ethyl]pyrrolidine 24 (from L-proline in six steps) reacted with 1 to afford the corresponding indolidinone 25 in 67% yield, which has previously been converted to allopumiliotoxin 267A.

  DOI：

  10.1021/ja970810j

文献信息

• Efficient and Practical Method for Synthesizing N-Heterocyclic Compounds Using Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by Ti(O-<i>i</i>-Pr)₄/2<i>i</i>-PrMgX Reagent. Synthesis of Quinolones, Pyrroles, Indoles, and Optically Active N-Heterocycles Including Allopumiliotoxin Alkaloid 267A
  作者：Sentaro Okamoto、Masayuki Iwakubo、Katsushige Kobayashi、Fumie Sato

  DOI：10.1021/ja970810j

  日期：1997.7.1

  Treatment of N-(2- or 3-alkynyl)amino esters with a low-valent titanium reagent diisopropoxy(eta(2)-propene)titanium (1), generated in situ by the reaction of Ti(O-i-Pr)(4) and 2i-PrMgCl, resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford alpha-alkylidene-pyrrolidinones or -piperidinones. Thus, treatment of N-propargyl-anthranilates 5, -indole-2-carboxylates 10, or -pyrrole-2-carboxylates 13 with 1 gave 4-quinolones 7, [1,2-a]indoles, or [1,2-a]pyrroles, respectively. Similarly, N-alkynylated alpha- or beta-amino esters 14 or 15 with 1 afforded N-heterocycles 18 or 19. In the reaction of N-(2- or 3-alkenyl)amino esters with 1, the resulting INAS product underwent intramolecular carbonyl addition (ICA) reaction to afford the N-heterocyclic compounds having a cyclopropanol moiety in good to excellent yields. Thus, the treatment of N-alkenyl-anthranilate 4a, -indole-2-carboxylates 8 and 9, or -pyrrole-2-carboxylates 11 and 12 with 1 gave the corresponding quinoline derivative 6a, [1,2-a]indoles, or [1,2-a]pyrroles, respectively. The optically active N-heterocyclic compounds 20 and 21 were obtained from N-alkenylated alpha- or beta-amino esters 16 or 17. A highly efficient total synthesis of allopumiliotoxin alkaloid 267A has also been accomplished. Thus, the N-propargyl-2[(1-hydroxy-1-methoxycarbonyl)ethyl]pyrrolidine 24 (from L-proline in six steps) reacted with 1 to afford the corresponding indolidinone 25 in 67% yield, which has previously been converted to allopumiliotoxin 267A.