N,N-Bis((R)-1-phenylethyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine | 712352-08-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: N,N-Bis((R)-1-phenylethyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine
• 英文别名: O,O'-(S)-(1,1'-dinaphthyl-2,2'-diyl)-N,N-di-(S,S)-[2-phenylethylphosphoramidite]；O,O'-(S)-(1,1'-dinaphthyl-2,2'-diyl)-N,N'-di-(S,S)-2-phenylethylphosphoramidite；O,O'-(S)-(1,1'-dinaphthyl-2,2'-diyl)-N,N'-di-(S,S)-[phenylethyl]phosphoramidite；O,O'-(S)-(1,1'-dinaphthyl-2,2'-diyl)-N,N'-di-(S,S)-[phenylethylphosphoramidite]；(Sa,S,S)-Monophos-pe；o,o'-(S)-(1,1'-dinaphthyl-2,2'-diyl)-N,N-di-(S,S)-1-phenylethylphophoramidite；(S,S,Sa)-(CH3CH(Ph))2NP(OC10H6C10H6O)；S,S,S-(PhC(Me))2NPOC10H6C10H6O；((P)-bis-naphthaleno[1,2-f;2,1-d]-1,3-dioxa-2-phosphacycloheptan-2-yl)-(S,S)-bis(1-phenylethyl)amine；O,O'-(P)-(1,1'-binaphthyl-2,2'-diyl)-N,N-(S,S)-bis(1-phenylethyl)phosphoramidite；((M)-bis-naphthaleno[1,2-f;2,1-d]-1,3-dioxa-2-phosphacycloheptan-2-yl)-(S,S)-bis(1-phenylethyl)amine；O,O'-(M)-(1,1'-binaphthyl-2,2'-diyl)-N,N-(S,S)-bis(1-phenylethyl)phosphoramidite；(Ra,S(C),S(C))-O,O'-[1,1'-binaphthyl-2,2'-diyl]-N,N-bis[1-phenylethyl]phosphoramidite；[(R)-1,1'-binaphthyl-2,2'-diyldioxy]{bis[(S)-(1-phenylethyl)]amino}phosphine；(S,S,S)-N,N-bis(1-phenylethyl)binaphtholphosphoramidite；(S,S,S)-(1,1'-binaphthyl-2,2'-dioxy)PN(CHMePh)2；(S,S,S)-(1,1'-binaphthyl)O2PN(1-phenethyl)2；(S,S,S)-binol-[N(CHCH3Ph)2] phosphoramidite；(S,S,S)-(Binol)PN(CHCH3Ph)2；(S,S,S)
• CAS: 712352-08-4；640720-25-8
• 化学式: C₃₆H₃₀NO₂P
• 分子量: 539.6
• InChiKey: LKZPDRCMCSBQFN-UIOOFZCWSA-N

物化性质

• 沸点：
  710.7±63.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.9
• 重原子数：
  40
• 可旋转键数：
  5
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2921499090

反应信息

• 作为产物：
  描述：

  双((S)-1-苯乙基)胺 、 (R)-(1,1′-联萘-2,2′-二氧)氯膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以95%的产率得到N,N-Bis((R)-1-phenylethyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine
  参考文献：
  名称：

  Efficient, Selective, and Green:  Catalyst Tuning for Highly Enantioselective Reactions of Ethylene

  摘要：

  Fine tuning of the biaryl and amino moieties of Feringa's phosphoramidite ligands yields structurally simpler, yet more efficient and selective, ligands for asymmetric hydrovinylation of vinylarenes and acylic 1,3-dienes. The enantioselectivities and yields observed in the formation of the 3-arylbutenes are among the highest for all asymmetric catalytic processes reported to date for the synthesis of intermediates for the widely used antiinflammatory 2-arylpropionic acids including naproxen, ibuprofen, fenoprofen, and flurbiprofen.

  DOI：

  10.1021/ol800395m
• 作为试剂：
  描述：

  氟双(苯基磺酰基)甲烷 、 3-(6-methoxynaphthalen-2-yl)allyl methyl carbonate 在 正丙胺 、 N,N-Bis((R)-1-phenylethyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 caesium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 以94%的产率得到2-[(2S)-1,1-bis(benzenesulfonyl)-1-fluorobut-3-en-2-yl]-6-methoxynaphthalene
  参考文献：
  名称：

  铱催化氟双（苯磺酰基）甲烷的区域和对映选择性烯丙基烷基化。

  摘要：

  [Ir（COD）Cl]（2）/亚磷酰胺实现了氟双（苯磺酰基）甲烷（FBSM）的高度区域和对映选择性烯丙基烷基化，提供了带有末端烯烃的对映体纯的氟双（苯磺酰基）甲基化化合物，可以将其转化只需两步即可制得单氟甲基化布洛芬，而不会损失光学纯度（95％ee）。

  DOI：

  10.1039/b914315g

文献信息

• Enantioselective Allylation of Alkenyl Boronates Promotes a 1,2-Metalate Rearrangement with 1,3-Diastereocontrol
  作者：Colton R. Davis、Irungu K. Luvaga、Joseph M. Ready

  DOI：10.1021/jacs.1c01242

  日期：2021.4.7

  Alkenyl boronates add to Ir(π-allyl) intermediates with high enantioselectivity. A 1,2-metalate shift forms a second C–C bond and sets a 1,3-stereochemical relationship. The three-component coupling provides tertiary boronic esters that can undergo multiple additional functionalizations. An extension to trisubstituted olefins sets three contiguous stereocenters.

  烯基硼酸盐添加到具有高对映选择性的 Ir(π-烯丙基) 中间体。1,2-金属酸盐位移形成第二个 C-C 键并建立 1,3-立体化学关系。三组分偶联提供了可以进行多种额外功能化的叔硼酸酯。三取代烯烃的延伸设置了三个连续的立体中心。
• Copper-Catalyzed Asymmetric Conjugate Addition of Trialkylaluminium Reagents to Trisubstituted Enones: Construction of Chiral Quaternary Centers
  作者：Magali Vuagnoux-d'Augustin、Alexandre Alexakis

  DOI：10.1002/chem.200701001

  日期：2007.11.26

  vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2-enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3CN)4]BF4 or [CuOTf]2C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous

  在催化作用下，Me3Al，Et3Al和乙烯基丙烷类物质进行对映选择性共轭加成，生成各种2-或3-取代的烯酮（环戊-2-烯酮，环己-2-烯酮，3-甲基环庚-2-烯酮）铜盐（噻吩羧酸铜，[Cu（CH3CN）4] BF4或[CuOTf] 2C6H6）和基于对位亚磷酰胺的配体。因此，经过严格优化实验条件后，可以建立具有高达98％ee的手性四元中心。结果表明，主要的重要参数是试剂引入的顺序。然后，将生成的对映体富集的烯醇铝和手性共轭加合物官能化并用于随后的反应。
• Enantioselective Syntheses of <i>Strychnos</i> and <i>Chelidonium</i> Alkaloids through Regio‐ and Stereocontrolled Cooperative Catalysis
  作者：Luke S. Hutchings‐Goetz、Chao Yang、James W. B. Fyfe、Thomas N. Snaddon

  DOI：10.1002/anie.202005151

  日期：2020.9.28

  We describe enantioselective syntheses of strychnos and chelidonium alkaloids. In the first case, indole acetic acid esters were established as excellent partner nucleophiles for enantioselective cooperative isothiourea/Pd catalyzed α‐alkylation. This provides products containing indole‐bearing stereocenters in high yield and with excellent levels of enantioinduction in a manner that is notably independent

  我们描述的对映选择性合成马钱子和白屈菜生物碱。在第一种情况下，吲哚乙酸酯被确定为对映选择性协同异硫脲/ Pd催化α-烷基化的优秀伴侣亲核试剂。这提供了以高收率和出色的对映体诱导水平包含吲哚的立构中心的产品，其方式明显独立于N取代基。这导致了（−）‐ akuammicine和（−）‐ strychnine的简明合成。在第二种情况下，邻位表现不佳对映选择性协同异硫脲/ Ir催化的α-烷基化反应中的预取代肉桂酸亲电试剂可通过适当的取代基选择来克服，从而导致（+）-螯合碱，（+）-去甲螯合碱和（+）-螯合胺的对映选择性合成。
• Enantioselective Catalytic Conjugate Addition of Dialkylzinc Reagents using Copper–Phosphoramidite Complexes; Ligand Variation and Non-linear Effects
  作者：Leggy A Arnold、Rosalinde Imbos、Alessandro Mandoli、André H.M de Vries、Robert Naasz、Ben L Feringa

  DOI：10.1016/s0040-4020(00)00142-3

  日期：2000.4

  cyclohexenone and chalcone in order to assess the structural features that are important for stereocontrol. A sterically demanding amine moiety is essential to reach high e.e.’s. Enantioselectivities for chalcones up to 89% and for cyclic enones up to 98% were found. Studies on non-linear effects with the best ligands for both cyclohexenone and chalcone showed clear non-linear effects for both cyclic

  合成了多种新的手性亚磷酰胺，并在铜催化的对乙基己烯酮和查耳酮的铜催化对映选择性共轭加成中进行了测试，以评估对立体控制至关重要的结构特征。空间要求高的胺部分对于达到高ee是必不可少的。发现查尔酮的对映选择性高达89％，环烯酮的对映选择性高达98％。对具有最佳配体的环己烯酮和查尔酮的非线性效应的研究表明，环状和非环状烯酮均具有明显的非线性效应。
• Iridium-Catalyzed Allylic Substitutions with Cyclometalated Phosphoramidite Complexes Bearing a Dibenzocyclooctatetraene Ligand: Preparation of (π-Allyl)Ir Complexes and Computational and NMR Spectroscopic Studies
  作者：Jevgenij A. Raskatov、Mascha Jäkel、Bernd F. Straub、Frank Rominger、Günter Helmchen

  DOI：10.1002/chem.201201772

  日期：2012.11.5

  (π‐Allyl)Ir complexes derived from dibenzocyclooctatetraene and phosphoramidites by cyclometalation are effective catalysts for allylic substitution reactions of linear monosubstituted allylic carbonates. These catalysts provide exceptionally high degrees of regioselectivity and allow the reactions to be run under aerobic conditions. A series of (π‐allyl)Ir complexes were prepared and characterized

  通过环金属化作用衍生自二苯并环辛酸酯和亚磷酰胺的（π-烯丙基）Ir络合物是线性单取代烯丙基碳酸酯的烯丙基取代反应的有效催化剂。这些催化剂具有极高的区域选择性，并允许反应在有氧条件下进行。制备了一系列（π-烯丙基）Ir配合物，并通过X射线晶体结构分析对其进行了表征。苯胺的烯丙基胺化反应取决于强碱的存在而显示出不同的静止状态。DFT计算是根据这些反应的机理进行的。结果表明，对于（π-烯丙基）Ir络合物，亲核试剂的形成和反应以相近的速率进行。