(1S,2R,5R,6R)-2-methoxy-5-vinyl-1-azabicyclo[3.2.2]nonane | 286368-37-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环庚烷
• 英文名称: (1S,2R,5R,6R)-2-methoxy-5-vinyl-1-azabicyclo[3.2.2]nonane
• 英文别名: (2R,5R,6R)-6-ethenyl-2-methoxy-1-azabicyclo[3.2.2]nonane
• CAS: 286368-37-4
• 化学式: C₁₁H₁₉NO
• 分子量: 181.278
• InChiKey: YGGKAOFGUGITCI-HBNTYKKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2R,5R,6R)-2-methoxy-5-vinyl-1-azabicyclo[3.2.2]nonane 在 叠氮基三甲基硅烷 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以81%的产率得到2-azido-6-vinyl-1-aza-bicyclo[3.2.2]nonane
  参考文献：
  名称：

  S_N1-like Reactions of Bicyclic α-Amino Ethers with Sulfur, Nitrogen, and Carbon Nucleophiles. Synthesis of 1-Azabicyclo[3.2.2]nonanes Functionalized at Carbon C2 and C6 with Complete Stereocontrol

  摘要：

  In the presence of nucleophiles, Lewis acid mediated cleavage of alpha-amino ethers derived from quincorine and quincoridine affords a variety of C2-substituted and C6-vinylated 1-azabicyclo[3.2.2]nonanes. These are enantiopure and are formed in S(N)1-like reactions with complete stereocontrol. There is no leakage into 2-Nu en route to product 1-Nu or vice versa. Me3SiCN provides new Strecker-type alpha-amino nitrilles. In the presence of TTMPP-BF3.OET2, the ketene acetal Me2C=C(OMe)OSiMe3 delivers enantiopure bicyclic beta-amino acid esters.

  DOI：

  10.1021/ol026342m
• 作为产物：
  描述：

  (1S,2S,4S,5R)-methanesulfonic acid 5-vinyl-1-azabicyclo-[2.2.2]oct-2-ylmetyl ester 在 silver benzoate 、 lithium iodide 作用下， 以 1,4-二氧六环 为溶剂， 反应 26.0h， 生成 (1S,2R,5R,6R)-2-methoxy-5-vinyl-1-azabicyclo[3.2.2]nonane
  参考文献：
  名称：

  Synthesis of Enantiopure 1-Azabicyclo[3.2.2]nonanes via Stereoselective Capture of Chiral Carbocations

  摘要：

  [GRAPHICS]A new class of doubly functionalized and enantiomerically pure 1-azabicyclo[3.2.2]nonanes derived from quincorine and quincoridine is described. 2,5-Disubstituted quinuclidines with a C9-mesyloxy group were easily transformed into the corresponding halides upon treatment with lithium salts. Subsequent silver salt-mediated ring expansion stereoselectively furnished the title azabicyclics. Chiral carbocations which are configurationally stable and nonplanar are postulated to account for the striking stereoselectivity of the capture of external nucleophile. 5-Ethynyl-2-iodomethylquinuclidines afford the alpha-benzoyloxy amines rather than alpha-methoxy amines, even in MeOH.

  DOI：

  10.1021/ol0057378

文献信息

• Synthesis of Enantiopure 1-Azabicyclo[3.2.2]nonanes via Stereoselective Capture of Chiral Carbocations
  作者：Stefanie Röper、Jens Frackenpohl、Olaf Schrake、Rudolf Wartchow、H. M. R. Hoffmann

  DOI：10.1021/ol0057378

  日期：2000.6.1

  [GRAPHICS]A new class of doubly functionalized and enantiomerically pure 1-azabicyclo[3.2.2]nonanes derived from quincorine and quincoridine is described. 2,5-Disubstituted quinuclidines with a C9-mesyloxy group were easily transformed into the corresponding halides upon treatment with lithium salts. Subsequent silver salt-mediated ring expansion stereoselectively furnished the title azabicyclics. Chiral carbocations which are configurationally stable and nonplanar are postulated to account for the striking stereoselectivity of the capture of external nucleophile. 5-Ethynyl-2-iodomethylquinuclidines afford the alpha-benzoyloxy amines rather than alpha-methoxy amines, even in MeOH.
• S_N1-like Reactions of Bicyclic α-Amino Ethers with Sulfur, Nitrogen, and Carbon Nucleophiles. Synthesis of 1-Azabicyclo[3.2.2]nonanes Functionalized at Carbon C2 and C6 with Complete Stereocontrol
  作者：Stefanie Röper、Rudolf Wartchow、H. Martin R. Hoffmann

  DOI：10.1021/ol026342m

  日期：2002.9.1

  In the presence of nucleophiles, Lewis acid mediated cleavage of alpha-amino ethers derived from quincorine and quincoridine affords a variety of C2-substituted and C6-vinylated 1-azabicyclo[3.2.2]nonanes. These are enantiopure and are formed in S(N)1-like reactions with complete stereocontrol. There is no leakage into 2-Nu en route to product 1-Nu or vice versa. Me3SiCN provides new Strecker-type alpha-amino nitrilles. In the presence of TTMPP-BF3.OET2, the ketene acetal Me2C=C(OMe)OSiMe3 delivers enantiopure bicyclic beta-amino acid esters.