(1R,8S)-1-chloromethyl-2,2-dichloro-3-oxo-hexahydropyrrolizidine | 141521-13-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯里西啶类
• 英文名称: (1R,8S)-1-chloromethyl-2,2-dichloro-3-oxo-hexahydropyrrolizidine
• 英文别名: (1R,7aS)-1-chloromethyl-2,2-dichloro-hexahydropyrrolizin-3-one；(1R,8S)-2,2-dichloro-1-(chloromethyl)-5,6,7,8-tetrahydro-1H-pyrrolizin-3-one
• CAS: 141521-13-3
• 化学式: C₈H₁₀Cl₃NO
• 分子量: 242.532
• InChiKey: NWIZMFGYLMKIGO-WDSKDSINSA-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：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1R,8S)-1-chloromethyl-2,2-dichloro-3-oxo-hexahydropyrrolizidine 在 palladium on activated charcoal 氢气 、 sodium acetate 、 sodium iodide 作用下， 以 乙醇 、 丁酮 为溶剂， 反应 24.0h， 生成 (1R,8S)-1-iodomethyl-3-oxo-hexahydropyrrolizidine
  参考文献：
  名称：

  Synthesis of pyrrolizidines via copper(I) catalyzed radical atom transfer cyclization

  摘要：

  Trachelanthamidine and pseudoheliotridane are synthesized from 2S)-N-trichlkoroacetyl-2-vinylpyrrolidine (5) by a 5-exo-trig radical cyclization. The intermediate radical is generated heating 5 in a sealed tube (CH3CN/ 160-degrees-C) using CuCl as catalyst and the cyclization occurs in very good yield (93%). Cyclized product 6 is transformed either into (-)-trachelanthamidine (55% yield from 5) or into (-)-pseudoheliotridane (42% yield from 5).

  DOI：

  10.1016/s0040-4020(01)88722-6
• 作为产物：
  描述：

  (S)-2-vinylpyrrolidine 在 4-二甲氨基吡啶 、 copper(l) chloride 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 2.0h， 生成 (1R,8S)-1-chloromethyl-2,2-dichloro-3-oxo-hexahydropyrrolizidine
  参考文献：
  名称：

  Synthesis of pyrrolizidines via copper(I) catalyzed radical atom transfer cyclization

  摘要：

  Trachelanthamidine and pseudoheliotridane are synthesized from 2S)-N-trichlkoroacetyl-2-vinylpyrrolidine (5) by a 5-exo-trig radical cyclization. The intermediate radical is generated heating 5 in a sealed tube (CH3CN/ 160-degrees-C) using CuCl as catalyst and the cyclization occurs in very good yield (93%). Cyclized product 6 is transformed either into (-)-trachelanthamidine (55% yield from 5) or into (-)-pseudoheliotridane (42% yield from 5).

  DOI：

  10.1016/s0040-4020(01)88722-6

文献信息

• Atom-transfer radical reactions catalyzed by a coordinatively unsaturated diruthenium amidinate, [(η5-C5Me5)Ru(μ2-i-PrN C(Me)Ni-Pr)Ru(η5-C5Me5)]+
  作者：Yukihiro Motoyama、Shiori Hanada、Shota Niibayashi、Kazuya Shimamoto、Naoki Takaoka、Hideo Nagashima

  DOI：10.1016/j.tet.2005.08.037

  日期：2005.10

  Atom-transfer radical cyclization (ATRC) and addition (ATRA) catalyzed by a coordinatively unsaturated diruthenium amidinate complex 4, [(η5-C5Me5)Ru(μ2-i-PrNC(Me)Ni-Pr)Ru(η5-C5Me5)]+, are investigated, and their features are compared with those of atom-transfer radical polymerization (ATRP). As an example of ATRC, a cationic diruthenium amidinate 4 is found to exhibit excellent catalytic reactivity

  由配位不饱和二钌催化原子转移自由基环化（ATRC）和加成（ATRA）脒基络合物4，[（η 5 -C 5我5）的Ru（μ 2 -我-PrNC（ME）N我-Pr）的Ru （η 5 -C 5我5）] +，进行了研究，它们的特征与那些原子转移自由基聚合（ATRP）的比较。作为ATRC的一个例子，发现阳离子di胺酸二钌4对N的环化具有极好的催化反应活性。-烯丙基α-卤代乙酰胺，包括环境温度下的生物碱骨架。从卤化物络合物原位产生的催化物种，（η 5 -C 5我5）的Ru（μ 2 -我-PrNC（ME）N我-Pr）的Ru（η 5 -C 5我5）（X）[ X = Cl，Br]和弱配位阴离子如NaPF 6和NaBPh 4的钠盐也显示出高催化活性。这实际上提供了解决作为实用催化剂的不稳定的4的解决方案。原位生成的催化剂种类4在室温下，α-烯烃对α，α，γ-三氯化γ-内酰胺与烯烃的分子间ATRA也有活性，以中等
• A Cationic Diruthenium Amidinate, [(η⁵-C₅Me₅)Ru(μ₂-<i>i</i>-PrN=C(Me)N<i>i</i>-Pr)Ru(η⁵-C₅Me₅)]⁺, as an Efficient Catalyst for the Atom-Transfer Radical Reactions
  作者：Yukihiro Motoyama、Mitsuru Gondo、Satoshi Masuda、Yuya Iwashita、Hideo Nagashima

  DOI：10.1246/cl.2004.442

  日期：2004.4

  A cationic diruthenium amidinate, [(η5-C5Me5)Ru(μ2-i-PrN=C(Me)Ni-Pr)Ru(η5-C5Me5)]+, is generated by treatment of (η5-C5Me5)Ru(μ2-i-PrN=C(Me)Ni-Pr)Ru(Cl)(η5-C5Me5) (3a) with NaPF6 or other metal salts of weakly coordinating anions, which is active towards catalytic atom transfer radical cyclization of N-allyl trichloroacetamides and related reactions.

  通过处理 (η5-C5Me5)Ru(μ2- 生成阳离子二钌脒盐，[(η5-C5Me5)Ru(μ2-i-PrN=C(Me)Ni-Pr)Ru(η5-C5Me5)]+ i-PrN=C(Me)Ni-Pr)Ru(Cl)(η5-C5Me5) (3a) 与 NaPF6 或其他弱配位阴离子的金属盐，对 N-烯丙基三氯乙酰胺的催化原子转移自由基环化具有活性相关反应。
• Ikeda, Masazumi; Teranishi, Hirotaka; Iwamura, Noriko, Heterocycles, 1997, vol. 45, # 5, p. 863 - 866
  作者：Ikeda, Masazumi、Teranishi, Hirotaka、Iwamura, Noriko、Ishibashi, Hiroyuki

  DOI：——

  日期：——
• Ngashima, Hideo; Gondo, Mitsuru; Masuda, Satoshi, Chemical Communications, 2003, # 3, p. 442 - 444
  作者：Ngashima, Hideo、Gondo, Mitsuru、Masuda, Satoshi、Kondo, Hideo、Yamaguchi, Yoshitaka、Matsubara, Kouki

  DOI：——

  日期：——
• Synthesis of pyrrolizidines via copper(I) catalyzed radical atom transfer cyclization
  作者：Julio A. Seijas、M.Pilar Vázquez-Tato、Luis Castedo、Ramón J. Estévez、M.Gabriela Ónega、Maria Ruíz

  DOI：10.1016/s0040-4020(01)88722-6

  日期：1992.2

  Trachelanthamidine and pseudoheliotridane are synthesized from 2S)-N-trichlkoroacetyl-2-vinylpyrrolidine (5) by a 5-exo-trig radical cyclization. The intermediate radical is generated heating 5 in a sealed tube (CH3CN/ 160-degrees-C) using CuCl as catalyst and the cyclization occurs in very good yield (93%). Cyclized product 6 is transformed either into (-)-trachelanthamidine (55% yield from 5) or into (-)-pseudoheliotridane (42% yield from 5).