N-(1-phenyl-2-propenyl)-4-methoxybenzylamine

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(1-phenyl-2-propenyl)-4-methoxybenzylamine
• 英文别名: N-[(4-methoxyphenyl)methyl]-1-phenylprop-2-en-1-amine
• 化学式: C₁₇H₁₉NO
• 分子量: 253.344
• InChiKey: KESVLELACHTZJA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(1-phenyl-2-propenyl)-4-methoxybenzylamine 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 二异丁基氢化铝 、 O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate 、 N,N-二异丙基乙胺 作用下， 以 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 88.0h， 生成 4-fluoro-1-[(4-methoxyphenyl)methyl]-2-phenyl-1H-pyrrole
  参考文献：
  名称：

  灵活合成多官能化的3-氟吡咯†

  摘要：

  从商业醛开始，已经开发了一种有效且选择性的合成多官能化3-氟吡咯的方法。该方法简明，有效并且允许模块化和系统地组装多取代的3-氟吡咯。这种合成为生成这些化学和生物学上重要的单元提供了另一种且高度收敛的策略。

  DOI：

  10.1039/c5ob02155c
• 作为产物：
  描述：

  3-苯基丙-2-烯-1-醇 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 吡啶 、 (3,5-Dioxa-4-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)-bis-((R)-1-phenyl-ethyl)-amine 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 生成 N-(1-phenyl-2-propenyl)-4-methoxybenzylamine
  参考文献：
  名称：

  铱-亚磷酰胺络合物催化的非手性烯丙基酯的区域和对映选择性烯丙基胺化

  摘要：

  通过探索手性亚磷酰胺的配合物，开发了一种新的催化不对称过程，即铱催化的 (E)-肉桂基和末端脂肪族烯丙基碳酸酯的对映选择性烯丙基胺化。该反应以高产率提供支链仲胺和叔烯丙胺，具有出色的区域选择性和对映选择性（13 个实例超过 94% ee）。尽管在极性溶剂如 DMF、EtOH 和 MeOH 中的反应速度很快，但它们的对映体过量率很低。相比之下，THF 中的反应显示出最合适的速率和对映选择性平衡。亚磷酰胺中的联萘单元和二取代胺均影响反应性和选择性，以及 O,O'-(R)-(1,1'-二萘基-2,2'-二基)-N,N'-di 的配合物-(R, R)-1-苯基乙基亚磷酰胺提供了最高的反应性和选择性。伯胺和环状仲胺在室温下反应，无环二乙胺在 50 摄氏度下反应。对甲氧基取代的肉桂基碳酸酯与未取代的肉桂基碳酸酯的反应类似，但邻甲氧基取代的底物产生较低的对映体过量。对于呋喃基-和烷基-取代的(E)-烯丙基碳酸酯反应的产物，也观察到高ee。

  DOI：

  10.1021/ja028614m

文献信息

• Enantioselective amination and etherification
  申请人：Hartwig F John

  公开号：US20060199728A1

  公开（公告）日：2006-09-07

  The present invention is directed to a catalyst composition, comprising: (1) a catalyst precursor having the general structure MSX n wherein M is a transition metal selected from the group consisting of iridium, molybdenum, and tungsten; S is a coordinating ligand; X is a counterion; and n is an integer from 0 to 5; and (2) a phosphoramidite ligand having the structure wherein O—C n —O is an aliphatic or aromatic diolate and wherein R 1 , R 2 , R 3 and R 4 are selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted aliphatic groups, and combinations thereof, with the proviso that at least one of R 1 , R 2 , R 3 , or R 4 must be a substituted or unsubstituted aryl or heteroaryl group. The present invention is also directed to activated catalysts made from the above catalyst composition, as well as methods of allylic amination and etherification using the above catalysts.

  本发明涉及一种催化剂组合物，包括：（1）具有一般结构MSXn的催化剂前体，其中M是从铱、钼和钨组成的过渡金属中选择的；S是一个配位配体；X是一个计数离子；n是从0到5的整数；以及（2）具有以下结构的磷酰胺配体，其中O-Cn-O是脂肪族或芳香族二醇，其中R1、R2、R3和R4选自取代或未取代的芳基基团、取代或未取代的杂环基团、取代或未取代的脂肪基团和它们的组合，但至少有一个R1、R2、R3或R4必须是取代或未取代的芳基或杂环基团。本发明还涉及由上述催化剂组合物制备的活性催化剂，以及使用上述催化剂进行烯丙基胺化和醚化的方法。
• Enantioselective Phosphoramidite Compounds and Catalysts
  申请人：Hartwig F. John

  公开号：US20070259774A1

  公开（公告）日：2007-11-08

  This invention relates to phosphoramidite compounds and catalyst complexes which can be used to provide enantioselective reactions including hydroamination reactions, etherification reactions and conjugate addition reactions and allylic substitution reactions, among others. In a first aspect, the present invention is directed to phosphoramidite and related compounds according to general structure (I), where Z is absent or is a group containing O, N or S, preferably O; R 1 and R 2 are independently an optionally substituted C 1-12 alkyl group, an optionally substituted (CH 2 ) n -aromatic group or (CH 2 ) n -heteroaromatic group, or are linked together to form an optionally substituted aliphatic or (CH 2 ) n -aromatic dianion of a diol, diamine, dithiol, aminoalcohol, aminohiolate or a alcoholthiol group; R 3′ and R 3 are each independently H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic group with the proviso that R 3′ and R 3 are not both H, or together R 3′ and R 3 form an optionally substituted C 5 -C 15 saturated or unsaturated carbocyclic ring; R 4 is H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic group; R 5 is absent, H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic or (CH 2 ) n -heteroaromatic group; R a and R a′ are each independently H or a C 1 -C 3 alkyl group, or R a and R a′ together with the carbon to which they are attached form a optionally substituted C 5 -C 15 saturated or unsaturated carbocyclic or heterocyclic ring, or an aromatic or heteroaromatic ring; R 6 and R 7 are each independently H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic group, with the proviso that R 5 , R 6 and R 7 cannot simultaneously be H, and when R a and R a′ , together with the carbon to which they are attached, form a carbocyclic ring, heterocyclic ring or an aromatic or heteroaromatic ring, R 5 is absent or is preferably H; R 6 and R 7 are preferably H or CH 3 ; and each n is independently 0, 1, 2, 3, 4, 5 or 6 and wherein at least one of the carbon atoms attached to the nitrogen of the phosphoramidite group is a chiral center.

  本发明涉及磷酰胺类化合物和催化剂复合物，可用于提供对映选择性反应，包括羟胺化反应、醚化反应和共轭加成反应以及联烯取代反应等。在第一个方面，本发明涉及磷酰胺和相关化合物，其一般结构如下（I），其中Z不存在或是包含O、N或S的基团，优选为O；R1和R2分别为可选取代的C1-12烷基、可选取代的（CH2）n-芳基或（CH2）n-杂芳基，或相互连接形成可选取代的脂肪族或（CH2）n-芳香基的二阴离子的二元醇、二胺、二硫醇、氨基醇、氨基硫醇或醇硫基基团；R3'和R3各自独立地为H、可选取代的C1-C12烷基或可选取代的（CH2）n-芳基，但须满足R3'和R3不能同时为H，或者R3'和R3共同形成可选取代的C5-C15饱和或不饱和的碳环；R4为H、可选取代的C1-C12烷基或可选取代的（CH2）n-芳基；R5不存在、为H、可选取代的C1-C12烷基或可选取代的（CH2）n-芳基或（CH2）n-杂芳基；Ra和Ra'各自独立地为H或C1-C3烷基，或者Ra和Ra'与它们附着的碳共同形成可选取代的C5-C15饱和或不饱和的碳环或杂环，或芳香或杂芳环；R6和R7各自独立地为H、可选取代的C1-C12烷基或可选取代的（CH2）n-芳基，但须满足R5、R6和R7不能同时为H，且当Ra和Ra'与它们附着的碳共同形成碳环、杂环或芳香或杂芳环时，R5不存在或优选为H；R6和R7优选为H或CH3；每个n独立地为0、1、2、3、4、5或6，其中至少有一个连接到磷酰胺基团氮上的碳原子是手性中心。
• US7732365B2
  申请人：——

  公开号：US7732365B2

  公开（公告）日：2010-06-08
• [EN] ENANTIOSELECTIVE AMINATION AND ETHERIFICATION___________________<br/>[FR] AMINATION ET ETHERIFICATION ENANTIOSELECTIVE
  申请人：UNIV YALE

  公开号：WO2004024684A2

  公开（公告）日：2004-03-25

  The present invention is directed to a catalyst composition, comprising: (1) a catalyst precursor having the general structure MSXn wherein M is a transition metal selected from the group consisting of iridium, molybdenum, and tungsten; S is a coordinating ligand; X is a counterion; and n is an integer from 0 to 5; and (2) a phosphoramidite ligand having the structure wherein O-Cn-O is an aliphatic or aromatic diolate and wherein R1, R2, R3 and R4 are selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted aliphatic groups, and combinations thereof, with the proviso that at least one of R1, R2, R3, or R4 must be a substituted or unsubstituted aryl or heteroaryl group. The present invention is also directed to activated catalysts made from the above catalyst composition, as well as methods of allylic amination and etherification using the above catalysts.
• Regio- and Enantioselective Allylic Amination of Achiral Allylic Esters Catalyzed by an Iridium−Phosphoramidite Complex
  作者：Toshimichi Ohmura、John F. Hartwig

  DOI：10.1021/ja028614m

  日期：2002.12.1

  asymmetric process, the iridium-catalyzed enantioselective allylic amination of (E)-cinnamyl and terminal aliphatic allylic carbonates, was developed by exploring complexes of chiral phosphoramidites. The reaction provided branched secondary and tertiary allylic amines in high yields with excellent regio- and enantioselectivity (13 examples over 94% ee). Although the reactions in polar solvent such as

  通过探索手性亚磷酰胺的配合物，开发了一种新的催化不对称过程，即铱催化的 (E)-肉桂基和末端脂肪族烯丙基碳酸酯的对映选择性烯丙基胺化。该反应以高产率提供支链仲胺和叔烯丙胺，具有出色的区域选择性和对映选择性（13 个实例超过 94% ee）。尽管在极性溶剂如 DMF、EtOH 和 MeOH 中的反应速度很快，但它们的对映体过量率很低。相比之下，THF 中的反应显示出最合适的速率和对映选择性平衡。亚磷酰胺中的联萘单元和二取代胺均影响反应性和选择性，以及 O,O'-(R)-(1,1'-二萘基-2,2'-二基)-N,N'-di 的配合物-(R, R)-1-苯基乙基亚磷酰胺提供了最高的反应性和选择性。伯胺和环状仲胺在室温下反应，无环二乙胺在 50 摄氏度下反应。对甲氧基取代的肉桂基碳酸酯与未取代的肉桂基碳酸酯的反应类似，但邻甲氧基取代的底物产生较低的对映体过量。对于呋喃基-和烷基-取代的(E)-烯丙基碳酸酯反应的产物，也观察到高ee。