tert-Butyl diazomalonyl chloride | 155193-73-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tert-Butyl diazomalonyl chloride
• 英文别名: tert-butyl diazo-malonylchloride；t-butyl 2-diazomalonyl chloride；t-butyl diazomalonyl chloride；tert-butyl (2E)-3-chloro-2-diazo-3-oxopropanoate
• CAS: 155193-73-0
• 化学式: C₇H₉ClN₂O₃
• 分子量: 204.613
• InChiKey: OREFXPAZEOCHOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  45.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-Butyl diazomalonyl chloride 在 dirhodium tetraacetate 对甲苯磺酸 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 6.0h， 生成 6-O-tert-butyl 3-O-methyl (3S)-8-acetyl-6-hydroxy-5-oxo-1,2,3,7-tetrahydroindolizine-3,6-dicarboxylate
  参考文献：
  名称：

  β-片层拟肽的6-氨基-5-氧-1,2,3,5-四氢-3-吲哚嗪羧酸的设计与合成

  摘要：

  6-氨基-5-氧代-1,2,3,5-四氢-3-吲哚嗪羧酸被设计为一种新型支架，可以有效模拟肽的延伸构象。支架合成中的关键反应涉及二羰基稳定的异丁烯酮中间体的[3 + 2]-环加成。通过制备有效的HCV NS3蛋白酶抑制剂证明了其作为β-折叠模拟物的有效性。

  DOI：

  10.1016/s0040-4039(02)02447-4
• 作为产物：
  描述：

  三光气 、 重氮基乙酸叔丁酯 在 吡啶 作用下， 以 苯 为溶剂， 以52%的产率得到tert-Butyl diazomalonyl chloride
  参考文献：
  名称：

  Studies on the Intramolecular Cycloaddition Reaction of Mesoionics Derived from the Rhodium(II)-Catalyzed Cyclization of Diazoimides

  摘要：

  A series of alkenyl-substituted imides were prepared by treating the appropriate amide with 2,2,6-trimethyl-4H-1,3-dioxen-4-one in xylene at 140-degrees-C to give the N-acetoacylated imides. Exposure of these imides to standard diazo transfer conditions gave the desired diazoimides. The carbenoid intermediate derived by treatment of the diazoimide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen atom to generate an isomunchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography. The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring pi-bond across the transient isomunchnone dipole. Molecular mechanics calculations were used to model energy differences between the endo and exo diastereomers. The calculations reveal that the endo diastereomers are significantly (8-12 kcal/mol) lower in energy than the corresponding exo isomers thereby providing a rationale for the preferred endo cycloaddition. Ring opening of the cycloadducts occurred readily producing a transient N-acyliminium ion which either lost a proton to give an enamide or was reduced by Et3SiH to afford a bicyclic piperidine ring.

  DOI：

  10.1021/jo00085a035

文献信息

• Studies on the intramolecular cycloaddition reaction of isomünchnones derived from N-alkenyl substituted diazoimides
  作者：Albert Padwa、David J. Austin、Alan T. Price、M. David Weingarten

  DOI：10.1016/0040-4020(95)01108-0

  日期：1996.2

  A series of N-alkenyl substituted diazoimides were prepared and subjected to Rh(II) catalyzed decomposition. The initially generated rhodium carbenoid undergoes ready cyclization onto the neighboring amide carbonyl oxygen atom to generate an isomünchnone intermediate. Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield. The stereochemical assignment

  制备了一系列的N-烯基取代的重氮酰亚胺，并进行了Rh（II）催化的分解。最初生成的铑类胡萝卜素经过适当的环化反应，形成相邻的酰胺羰基氧原子，以生成异氰基酮中间体。随后通过侧链烯烃的1，3-偶极环加成以高收率提供了环加合物。通过X射线晶体学推论了几种环加合物的立体化学分配。该反应的立体化学结果是的结果外跨过暂态isomünchnone偶极相邻π键的-环。分子力学计算被用来在模型之间的能量差外和内非对映体。计算表明exo非对映异构体的能量要比相应的内聚异构体低（18-20 kcal / mol），因此为优选的exo- cycloaddition提供了理论依据。
• Synthesis of polyheterocyclic ring compounds by the intramolecular cycloaddition of N-alkenyl substituted diazoimides
  作者：Albert Padwa、David J. Austin、Alan T. Price

  DOI：10.1016/0040-4039(94)85349-5

  日期：1994.9

  Rhodium(II) catalysis of various diazoimides containing tethered π-systems attached to the nitrogen atom results in isomünchnone dipole formation followed by intramolecular dipolar-cycloaddition.

  铑（II）催化的各种含重氮原子连接到氮原子上的π系统重氮酰亚胺，都会形成异丁烯酮偶极子，然后分子内偶极环加成。
• Amino-bicyclic pyrazinones and pyridinones as coagulation serine protease inhibitors
  申请人：Zhang Xiaojun

  公开号：US20050038030A1

  公开（公告）日：2005-02-17

  The present invention relates generally to compounds that inhibit serine proteases. In particular it is directed to novel amino-bicyclic pyrazinone and pyridinone compounds of Formula (I): or a stereoisomer or pharmaceutically acceptable salt form thereof, which are useful as selective inhibitors of serine protease enzymes of the coagulation cascade; for example thrombin, factor Xa, factor XIa, factor IXa, and/or factor VIIa. In particular, it relates to compounds that are factor VIIa inhibitors. This invention also relates to pharmaceutical compositions comprising these compounds and methods of using the same.

  本发明涉及一般用于抑制丝氨酸蛋白酶的化合物。特别是，本发明涉及公式（I）的新型氨基双环吡唑酮和吡啶酮化合物，或其立体异构体或药学上可接受的盐形式，其作为凝血级联反应中的丝氨酸蛋白酶酶类的选择性抑制剂具有用途，例如凝血酶、因子Xa、因子XIa、因子IXa和/或因子VIIa。特别是，本发明涉及因子VIIa抑制剂化合物。本发明还涉及包括这些化合物的制药组合物以及使用它们的方法。
• Ethyl 2-diazomalonyl chloride. An efficient diazoacylating reagent
  作者：Joseph P. Marino、Martin H. Osterhout、Alan T. Price、Scott M. Sheehan、Albert Padwa

  DOI：10.1016/s0040-4039(00)75980-6

  日期：1994.1

  Ethyl 2-diazomalonyl chloride readily reacts with aromatic and aliphatic amines, alcohols, thiols, and amides for form a variety of alpha-diazo carbonyl species.
• AMINO-BICYCLIC PYRAZINONES AND PYRIDINONES AS COAGULATION SERINE PROTEASE INHIBITORS
  申请人：Bristol-Myers Squibb Company

  公开号：EP1523483A2

  公开（公告）日：2005-04-20