2-(Hydroxy-phenyl-amino)-cycloheptanone

• 分子结构分类: 有机化合物 - 苯类化合物 - N-苯基羟胺
• 英文名称: 2-(Hydroxy-phenyl-amino)-cycloheptanone
• 英文别名: 2-(N-Hydroxyanilino)cycloheptanone；2-(N-hydroxyanilino)cycloheptan-1-one
• 化学式: C₁₃H₁₇NO₂
• 分子量: 219.283
• InChiKey: YCNAFURNGIDZHW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  40.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  环庚酮 在 trimethyltin methoxide 、 对甲苯磺酸 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 生成 2-(Hydroxy-phenyl-amino)-cycloheptanone
  参考文献：
  名称：

  Catalytic Enantioselective Synthesis of α-Aminooxy and α-Hydroxy Ketone Using Nitrosobenzene

  摘要：

  The highly enantioselective and O-selective nitroso aldol reaction of tin enolates 2 and nitrosobenzene (1) has been developed with the use of (R)-BINAP-silver complexes as a catalyst. After the various silver salts were surveyed, the AgOTf and the AgClO4 complex were found to be optimal in the O-selective nitroso aldol reaction in both asymmetric induction (up to 97% ee) and regioselection (O/N = >99/1), affording aminooxy ketone 3. The product 3 can be transformed to alpha-hydroxy ketone 5 without any loss of enantioselectivity. Thus, the method provides an efficient approach to the catalytic enantioselective introduction of oxygen alpha- to the carbonyl group.

  DOI：

  10.1021/ja0298702

文献信息

• Enantioselective <i>O</i>- and <i>N</i>-Nitroso Aldol Synthesis of Tin Enolates. Isolation of Three BINAP−Silver Complexes and Their Role in Regio- and Enantioselectivity
  作者：Norie Momiyama、Hisashi Yamamoto

  DOI：10.1021/ja039103i

  日期：2004.5.1

  ratio and/or choice of silver salt. Indeed, the X-ray crystallographic study has been used to gain insight into the structure of the catalyst. After the evaluation of each species, 1:1 (AgX.(R)-BINAP) complex was found to be the real active species in the O-selective nitroso aldol reaction. On the other hand, a systematic survey of solvent has shown that the optimal 2:1 (AgX.(R)-BINAP) complex is the effective

  通过金属/配体比例的适当组合和/或银盐的选择，实现了三种不同银-BINAP 催化剂的选择性生成。事实上，X 射线晶体学研究已被用于深入了解催化剂的结构。在对每种物质进行评估后，发现 1:1 (AgX.(R)-BINAP) 复合物是 O-选择性亚硝基醛醇反应中真正的活性物质。另一方面，对溶剂的系统调查表明，最佳的 2:1 (AgX.(R)-BINAP) 配合物是 N-选择性途径中的有效催化剂。因此，银-BINAP 催化剂的新生成方法和合成转化不仅为催化对映选择性亚硝基羟醛合成的发展领域提供了新的见解，而且为有效催化剂的设计提供了明确的指导。
• Simple Synthesis of α-Hydroxyamino Carbonyl Compounds:  New Scope of the Nitroso Aldol Reaction
  作者：Norie Momiyama、Hisashi Yamamoto

  DOI：10.1021/ol026443k

  日期：2002.10.1

  [reaction: see text] The reaction of nitroso compounds with enolates, "the nitroso aldol reaction", occurs in high yield to generate alpha-hydroxyamino carbonyl compounds. Yields range from 42% to 98% with N-selectivity >99:1 from commercially available aromatic or aliphatic nitroso compounds and a variety of alkali metal or tin enolates.

  [反应：见正文]亚硝基化合物与烯醇化物的反应，即“亚硝基羟醛反应”，以高收率发生，生成α-羟氨基羰基化合物。从市售的芳族或脂族亚硝基化合物和各种碱金属或烯醇锡的收率范围为42％至98％，N选择性> 99：1。
• Enantioselective Nitroso Aldol Reaction Catalyzed by QuinoxP*·Silver(I) Complex and Tin Methoxide
  作者：Akira Yanagisawa、Satoshi Takeshita、Youhei Izumi、Kazuhiro Yoshida

  DOI：10.1021/ja910588w

  日期：2010.4.21

  A catalytic enantioselective O-nitroso aldol reaction of alkenyl trichloroacetates with nitrosoarenes was achieved using the (R,R)-t-Bu-QuinoxP*.AgOAc complex as the chiral catalyst and Bu(2)Sn(OMe)(2) as the achiral cocatalyst in the presence of methanol. Optically active alpha-aminooxy ketones with up to 99% ee were regioselectively obtained in high yields from various alkenyl trichloroacetates of

  使用 (R,R)-t-Bu-QuinoxP*.AgOAc 配合物作为手性催化剂和 Bu(2)Sn(OMe)(2) 作为手性催化剂，实现了烯基三氯乙酸酯与亚硝基芳烃的催化对映选择性 O-亚硝基羟醛反应在甲醇存在下的非手性助催化剂。具有高达 99% ee 的光学活性 α-氨基氧基酮以高产率从环酮的各种烯基三氯乙酸酯中获得。
• Thieme Chemistry Journal Awardees - Where are They Now? Dibutyltin Dimethoxide Catalyzed <i>N</i>-Nitrosoaldol Reaction of Alkenyl Trichloroacetate
  作者：Akira Yanagisawa、Youhei Izumi、Satoshi Takeshita

  DOI：10.1055/s-0028-1087815

  日期：——

  Nitrosoaldol reaction between alkenyl trichloroacetates and nitrosobenzene has been achieved using dibutyltin dimethoxide as a catalyst, which is regenerated in the presence of methanol. The corresponding α-hydroxyamino ketones (N-adducts) have exclusively formed not only from cyclic alkenyl trichloroacetates but also from acyclic ones.

  以二甲醇二丁基锡为催化剂，在甲醇存在下再生，实现了烯基三氯乙酸酯与亚硝基苯之间的亚硝基醛醇反应。相应的α-羟基氨基酮（N-加合物）不仅由环状三氯乙酸烯基酯形成，而且还由非环状链烯基形成。