(+)-N-benzyl-1-(furan-2-yl)prop-2-en-1-amine

• 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-benzyl-1-(furan-2-yl)prop-2-en-1-amine
• 英文别名: N-[1-(2-furyl)-2-propenyl]benzylamine；N-benzyl-1-(2-furyl)-2-propen-1-amine；N-benzyl-1-(furan-2-yl)prop-2-en-1-amine
• 化学式: C₁₄H₁₅NO
• 分子量: 213.279
• InChiKey: PDUDEROCSCAUPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  25.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  反-3-(2-呋喃基)丙烯醛 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 、 二异丁基氢化铝 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 生成 (+)-N-benzyl-1-(furan-2-yl)prop-2-en-1-amine
  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。
• Effects of Catalyst Activation and Ligand Steric Properties on the Enantioselective Allylation of Amines and Phenoxides
  作者：Andreas Leitner、Chutian Shu、John F. Hartwig

  DOI：10.1021/ol050029d

  日期：2005.3.1

  The yields, enantioselectivities, and regioselectivities of the reactions of amines and phenoxides with allylic carbonates in the presence of a metallacyclic iridium catalyst were compared. These data show that both preactivation of the catalyst and the size of the ligand affect the yield, enantioselectivity, and regioselectivity. With the activated catalyst containing a bis-naphthethylamino group, the allylic amination and etherification of a broad range of allylic carbonates occurred in high yields and with high regioselectivities and enantioselectivities.
• Dondoni A., Merchan F. L., Merino P., Tejero T., Synth. Commun, 24 (1994) N 18, S 2551-2555
  作者：Dondoni A., Merchan F. L., Merino P., Tejero T.

  DOI：——

  日期：——
• 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.