(R)-1,1'-binaphthyl-2,2'-diyl phosphoramidate

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-1,1'-binaphthyl-2,2'-diyl phosphoramidate
• 英文别名: 13-Oxo-12,14-dioxa-13lambda5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-amine；13-oxo-12,14-dioxa-13λ5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-amine
• 化学式: C₂₀H₁₄NO₃P
• 分子量: 347.31
• InChiKey: WILHLIZSYLOYKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  61.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-1,1'-binaphthyl-2,2'-diyl phosphoramidate 、 (R)-1,1'-binaphthalene-2,2'-diyl phosphoric acid chloride 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 1.0h， 以79%的产率得到(11b'R)-4,4'-azanediylbis(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine 4-oxide)
  参考文献：
  名称：

  双轴向手性双磷酸酯类化合物催化吲哚与亚胺类的高度对映选择性和高效Friedel-Crafts反应

  摘要：

  凉爽的猫：1,1'-Bi-2-萘酚和拱形3,3'-联苯酚型双磷酸酰亚胺使催化剂和低催化剂负载的吲哚和N-甲苯磺胺之间能够进行原子经济且对映选择性高的Friedel-Crafts反应（参见方案） ）。极少量的4-（二甲基氨基）吡啶（DMAP）可有效抑制双吲哚副产物。的邻位-取代的醛亚胺基材在此催化体系进行良好。

  DOI：

  10.1002/chem.201202900
• 作为产物：
  描述：

  (R)-1,1'-binaphthalene-2,2'-diyl phosphoric acid chloride 在 sodium azide 、 palladium 10% on activated carbon 、 氢气 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 20.0 ℃ 、303.99 kPa 条件下， 反应 6.0h， 生成 (R)-1,1'-binaphthyl-2,2'-diyl phosphoramidate
  参考文献：
  名称：

  Double axially chiral bisphosphorylimides as novel Brønsted acids in asymmetric three-component Mannich reaction

  摘要：

  A double axially chiral bisphosphorylimide has been demonstrated to be an efficient and highly sterically hindered Bronsted acid in asymmetric three-component Mannich reactions. Optically active syn-beta-amino ketones were obtained in high yields (up to 99%) with excellent diastereoselectivity (99:1) and enantioselectivity (up to 99% ee). A gram-scale reaction was also performed to prove the synthetic application value of this reaction. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.06.008
• 作为试剂：
  描述：

  碘苯 、 3-(4-chlorophenyl)-N-(quinolin-8-yl)propanamide 在 双(乙腈)氯化钯(II) 、 (R)-1,1'-binaphthyl-2,2'-diyl phosphoramidate 、 caesium carbonate 作用下， 以 对二甲苯 为溶剂， 反应 12.25h， 以61%的产率得到
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Arylation of C(sp³)–H Bonds of Aliphatic Amides: Controlling Enantioselectivity Using Chiral Phosphoric Amides/Acids

  摘要：

  Enantioselective arylation of secondary beta-C(sp(3))-H bonds of 8-aminoquinoline amides was realized with a palladium catalyst. Chiral phosphoric amides and acids were used for the first time to control the stereoselectivity at the C-H bond cleavage step in the C-H activation reactions.

  DOI：

  10.1021/acs.orglett.5b00968

文献信息

• Chiral N-phosphoryl imines: design, synthesis and direct asymmetric addition reactions with diketones and diesters
  作者：Hao Sun、Trideep Rajale、Yi Pan、Guigen Li

  DOI：10.1016/j.tetlet.2010.06.072

  日期：2010.8

  Chiral N-phosphoryl imines derived from (S)-BINOL have been designed and synthesized in good to excellent chemical yields. These N-phosphoryl imines were found to react with diketones smoothly without the use of any bases. They can also serve as electrophiles for the reaction with diethyl malonate in the presence of potassium carbonate. Good yields (62%—quant) and excellent diastereoselectivities (up

  由（S）-BINOL衍生的手性N-磷酰基亚胺已经以良好的化学收率设计和合成。发现这些N-磷酰基亚胺在不使用任何碱的情况下与二酮平滑反应。它们还可以用作亲电子试剂，在碳酸钾存在下与丙二酸二乙酯反应。对于10个实例，已经获得了良好的收率（62％-定量）和出色的非对映选择性（高达99：1 dr）。
• [EN] STRECKER REAGENTS, THEIR DERIVATIVES, METHODS FOR FORMING THE SAME AND IMPROVED STRECKER REACTION<br/>[FR] RÉACTIFS DE STRECKER, LEURS DÉRIVÉS, PROCÉDÉS POUR LES FORMER ET RÉACTION DE STRECKER AMÉLIORÉE
  申请人：NOWA PHARMACEUTICALS CO LTD

  公开号：WO2011116530A1

  公开（公告）日：2011-09-29

  Strecker reagents, their derivatives and methods for forming the same and improved Strecker reaction are provided. The electrophiles for asymmetric Strecker reaction include achiral N-phosphorazides, N-phosphoramides, N-phosphonyl imines and their derivatives. The nucleophiles for asymmetric Strecker reaction include chiral BINOL-derived azides, amides, imines and their derivatives, the chiral and achiral diol-based cyanides and their derivatives, the chiral and achiral diamine-based cyanides and their derivatives, the chiral and achiral amino alcohol-based cyanides and their derivatives, the Strecker nucleophiles that are derived from chiral and achiral hydroxyl carboxylic acids and amino acids. Methods of forming the electrophile for asymmetric Strecker reaction comprise the reactions with steps of: a) synthesizing phosphoryl chloride from achiral diamine; b) synthesizing phosphorous azide; c) synthesizing phosphoramide; d) synthesizing the corresponding achiral N-phosphonyl imines. The asymmetric catalytic Strecker reaction of new achiral N-phosphonyl imines has been developed to give excellent enantioselectivity (up to >99%ee) and yields (up to >97%).

  提供了Strecker试剂、它们的衍生物以及形成相同和改进的Strecker反应的方法。用于不对称Strecker反应的亲电试剂包括非手性N-磷酰胺、N-磷酰胺、N-磷酰亚胺及其衍生物。用于不对称Strecker反应的亲核试剂包括手性BINOL衍生的叠氮化物、酰胺、亚胺及其衍生物，手性和非手性二醇基氰化物及其衍生物，手性和非手性二胺基氰化物及其衍生物，手性和非手性氨基醇基氰化物及其衍生物，以及源自手性和非手性羟基羧酸和氨基酸的Strecker亲核试剂。形成不对称Strecker反应亲电试剂的方法包括以下步骤的反应：a) 从非手性二胺合成磷酰氯；b) 合成磷氮化物；c) 合成磷酰胺；d) 合成相应的非手性N-磷酰亚胺。新的非手性N-磷酰亚胺的不对称催化Strecker反应已经发展出优异的对映选择性（高达>99%ee）和产率（高达>97%）。
• STRECKER REAGENTS, THEIR DERIVATIVES, METHODS FOR FORMING THE SAME AND IMPROVED STRECKER REACTION
  申请人：Li Guigen

  公开号：US20130137889A1

  公开（公告）日：2013-05-30

  Strecker reagents, their derivatives and methods for forming the same and improved Strecker reaction are provided. The electrophiles for asymmetric Strecker reaction include achiral N-phosphorazides, N-phosphoramides, N-phosphonyl imines and their derivatives. The nucleophiles for asymmetric Strecker reaction include chiral BINOL-derived azides, amides, imines and their derivatives, the chiral and achiral diol-based cyanides and their derivatives, the chiral and achiral diamine-based cyanides and their derivatives, the chiral and achiral amino alcohol-based cyanides and their derivatives, the Strecker nucleophiles that are derived from chiral and achiral hydroxyl carboxylic acids and amino acids. Methods of forming the electrophile for asymmetric Strecker reaction comprise the reactions with steps of: a) synthesizing phosphoryl chloride from achiral diamine; b) synthesizing phosphorous azide; c) synthesizing phosphoramide; d) synthesizing the corresponding achiral N-phosphonyl imines. The asymmetric catalytic Strecker reaction of new achiral N-phosphonyl imines has been developed to give excellent enantioselectivity (up to >99% ee) and yields (up to >97%).

  提供了Strecker试剂及其衍生物以及形成它们和改进的Strecker反应的方法。用于不对称Strecker反应的亲电试剂包括非手性N-磷酰胺、N-磷酰胺、N-磷酰亚胺及其衍生物。用于不对称Strecker反应的亲核试剂包括手性BINOL衍生的叠氮化物、酰胺、亚胺及其衍生物，手性和非手性二醇基氰化物及其衍生物，手性和非手性二胺基氰化物及其衍生物，手性和非手性氨基醇基氰化物及其衍生物，来源于手性和非手性羟基羧酸和氨基酸的Strecker亲核试剂。形成不对称Strecker反应的亲电试剂的方法包括以下步骤的反应：a)从非手性二胺合成磷酰氯；b)合成磷氮化物；c)合成磷酰胺；d)合成相应的非手性N-磷酰亚胺。新的非手性N-磷酰亚胺的不对称催化Strecker反应已经发展出具有优异的对映选择性（高达>99% ee）和产率（高达>97%）。
• Double axially chiral bisphosphorylimides as novel Brønsted acids in asymmetric three-component Mannich reaction
  作者：Ying-Ying Chen、Yi-Jun Jiang、Yan-Sen Fan、Di Sha、Qifeng Wang、Guangliang Zhang、Liangyu Zheng、Suoqin Zhang

  DOI：10.1016/j.tetasy.2012.06.008

  日期：2012.6

  A double axially chiral bisphosphorylimide has been demonstrated to be an efficient and highly sterically hindered Bronsted acid in asymmetric three-component Mannich reactions. Optically active syn-beta-amino ketones were obtained in high yields (up to 99%) with excellent diastereoselectivity (99:1) and enantioselectivity (up to 99% ee). A gram-scale reaction was also performed to prove the synthetic application value of this reaction. (c) 2012 Elsevier Ltd. All rights reserved.
• Double Axially Chiral Bisphosphorylimides Catalyzed Highly Enantioselective and Efficient Friedel-Crafts Reaction of Indoles with Imines
  作者：Kun Wu、Yi-Jun Jiang、Yan-Sen Fan、Di Sha、Suoqin Zhang

  DOI：10.1002/chem.201202900

  日期：2013.1.7

  Cool cats: 1,1′‐Bi‐2‐naphthol and vaulted 3,3′‐biphenanthrol‐type bisphosphorylimides enabled the atom‐economical and highly enantioselective Friedel–Crafts reaction between indoles and N‐tosylimines with a low catalyst loading (see scheme). A very small amount of 4‐(dimethylamino)pyridine (DMAP) suppressed the bisindole side product efficiently. The ortho‐substituted aldimine substrates performed

  凉爽的猫：1,1'-Bi-2-萘酚和拱形3,3'-联苯酚型双磷酸酰亚胺使催化剂和低催化剂负载的吲哚和N-甲苯磺胺之间能够进行原子经济且对映选择性高的Friedel-Crafts反应（参见方案） ）。极少量的4-（二甲基氨基）吡啶（DMAP）可有效抑制双吲哚副产物。的邻位-取代的醛亚胺基材在此催化体系进行良好。