(11bS)-8,9,10,11,12,13,14,15-八氢-N,N-二甲基联萘并[2,1-d:1',2'-f][1,3,2]二氧磷杂七环-4-胺 | 389130-06-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 中文名称: (11bS)-8,9,10,11,12,13,14,15-八氢-N,N-二甲基联萘并[2,1-d:1',2'-f][1,3,2]二氧磷杂七环-4-胺
• 中文别名: (S)-(+)-(8,9,10,11,12,13,14,15-八氢-3,5-二氧-4-PHOSPHA-环庚[2,1-一3,4-一']；二-Α-萘二亚胺- 4；(S)-(+)-(8,9,10,11,12,13,14,15-辛氢-3,5-二氧杂-4-磷杂-环庚[2,1-a；3,4-a']二萘-4-基)二甲基胺
• 英文名称: (S)-(+)-(8,9,10,11,12,13,14,15-octahydro-3,5-dioxa-4-phospha-cyclohepta[2,1-a:3,4-a']dinaphthalen-4-yl)dimethylamine
• 英文别名: (8,9,10,11,12,13,14,15-octahydro-3,5-dioxa-4-phospha-cyclohepta[2,1-a:3,4-a']dinaphthalen-4-yl)dimethylamine；H8-MonoPhos；N,N-dimethyl-12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3(8),9,16,18(23)-hexaen-13-amine
• CAS: 389130-06-7
• 化学式: C₂₂H₂₆NO₂P
• 分子量: 367.428
• InChiKey: OIZQADYWBXZQKE-UHFFFAOYSA-N

物化性质

• 熔点：
  112-113°C
• 比旋光度：
  +318° (c 0.63, THF)
• 沸点：
  523.3±60.0 °C(Predicted)
• 稳定性/保质期：
  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  26
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• WGK Germany：
  3
• 危险性防范说明：
  P261,P280,P301+P312,P302+P352,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  密封在阴凉干燥的环境中。

反应信息

• 作为反应物：
  描述：

  (11bS)-8,9,10,11,12,13,14,15-八氢-N,N-二甲基联萘并[2,1-d:1',2'-f][1,3,2]二氧磷杂七环-4-胺 在 selenium 作用下， 以 氘代氯仿 为溶剂， 生成
  参考文献：
  名称：

  使用单齿亚磷酰胺铱催化氢化β-脱氢氨基酸衍生物

  摘要：

  已经研究了铱催化的 13 种不同的 β-脱氢氨基酸衍生物的不对称氢化，以产生具有旋光活性的 β-氨基酸酯。容易获得的基于单齿八氢联萘酚的亚磷酰胺用作手性配体。E 异构体的对映选择性和产率非常好，而 Z 异构体的催化剂性能较差。重要的是，为了获得高对映选择性，必须在配体的 3,3' 位进行取代。在优化条件下实现了高达 94 % ee 的对映选择性。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  DOI：

  10.1002/ejoc.200800241
• 作为产物：
  描述：

  二甲胺 、 (11bR)-4-chloro-8,9,10,11,12,13,14,15-octahydrodinaphtho[2,1-d:1',2'-f]-[1,3,2]dioxaphosphepine 在 base 作用下， 以 四氢呋喃 为溶剂， 生成 (11bS)-8,9,10,11,12,13,14,15-八氢-N,N-二甲基联萘并[2,1-d:1',2'-f][1,3,2]二氧磷杂七环-4-胺
  参考文献：
  名称：

  Influence of Phosphoramidites in Copper-Catalyzed Conjugate Borylation Reaction

  摘要：

  Copper(I) has become the preferred metal to catalyze the beta-boration of alpha,beta-unsaturated carbonyl compounds, and now we demonstrate that easily accessible monodentate chiral ligands, such as phosphoramidites and phosphites, can be convenient alternative ligands to induce asymmetry in the enantioselective version of this reaction, particularly in the beta-boration of alpha,beta-unsaturated imines.

  DOI：

  10.1021/om300194k
• 作为试剂：
  描述：

  2-(tert-butyl-dimethyl-silanyloxymethyl)-prop-2-en-1-ol 在 4-二甲氨基吡啶 、 sodium perborate tetrahydrate 、 四溴化碳 、 三乙胺 、 三苯基膦 、 copper(I) bromide 、 lithium tert-butoxide 、 (11bS)-8,9,10,11,12,13,14,15-八氢-N,N-二甲基联萘并[2,1-d:1',2'-f][1,3,2]二氧磷杂七环-4-胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 36.0h， 生成
  参考文献：
  名称：

  铜催化的宝石二硼烷烃的对映基团选择性烯丙基化

  摘要：

  我们报告了铜催化的对映基团选择性烯丙基化的 gem-二硼烷烃与烯丙基溴。溴化铜 (I) 和 H8-BINOL 衍生的亚磷酰胺配体的组合被证明是提供各种对映体富集的高烯丙基硼酸酯的最有效的催化系统在温和条件下具有高对映体比率。已经进行了实验和理论研究以阐明反应机理，揭示了宝石-二硼烷基烷烃与手性铜配合物的对映基团选择性转移金属是如何发生手性 α-硼烷基-铜物种的。还包括合成各种手性构件的其他合成应用。

  DOI：

  10.1021/jacs.0c11750

文献信息

• Monodentate Phosphoramidites: A Breakthrough in Rhodium-Catalysed Asymmetric Hydrogenation of Olefins
  作者：Michel van den Berg、Adriaan J. Minnaard、Robert M. Haak、Michel Leeman、Ebe P. Schudde、Auke Meetsma、Ben L. Feringa、André H. M. de Vries、C. Elizabeth P. Maljaars、Charlotte E. Willans、David Hyett、Jeroen A. F. Boogers、Hubertus J. W. Henderickx、Johannes G. de Vries

  DOI：10.1002/adsc.200390026

  日期：2003.1

  ligands for the rhodium-catalysed asymmetric hydrogenation of olefins. Very high enantioselectivities were obtained with MonoPhos (7a) the simplest member of this class, a ligand that is prepared in a single step from BINOL and HMPT. Turnover numbers up to 6000 have been obtained in the hydrogenation of dehydroamino acid derivatives. Enantioselectivities in the hydrogenation of dehydroamino acids are solvent

  基于BINOL或取代BINOL的单齿亚磷酰胺是铑催化烯烃不对称氢化的出色配体。用MonoPhos（7a获得了很高的对映选择性）此类中最简单的成员，它是由BINOL和HMPT一步合成的配体。在脱氢氨基酸衍生物的氢化中，已经获得了高达6000的营业额。脱氢氨基酸加氢中的对映选择性取决于溶剂。在非质子溶剂中，它们的含量范围为95–99％。衣康酸及其二甲酯可以分别用96％ee和94％ee氢化。芳香族酰胺的氢化反应在86-94％ee中得到相应的酰化胺。已经制备了几种类似的亚磷酰胺配体。出人意料的是，就速率和对映选择性而言，双齿配体均给出较差的结果。基于Taddol的亚磷酰胺导致ee较差并降低速度。3处的甲基取代基 BINOL的3'-位置导致速率急剧降低，对映选择性略低。在6,6'-位的溴取代基导致速率略有降低，但对映选择性几乎没有影响。八氢-MonoPhos（11）得出的结果与用7a获得的结果非常相
• Diastereo- and Enantioselective Synthesis of Homoallylic Amines Bearing Quaternary Carbon Centers
  作者：Jacob C. Green、Joseph M. Zanghi、Simon J. Meek

  DOI：10.1021/jacs.9b11529

  日期：2020.1.29

  A Cu-catalyzed method for the efficient enantio- and diastereoselective synthesis of chiral homoallylic amines bearing a quaternary carbon and an alkenylboron is disclosed. Transformations are promoted by a readily prepared (phosphoramidite)-Cu complex, and involve bench-stable γ,γ,-disubstituted allyldiborons and benzyl imines; products are obtained in up to 82% yield, >20:1 dr, and >99:1 er. Reactions

  公开了一种用于有效对映选择性和非对映选择性合成带有季碳和烯基硼的手性高烯丙基胺的铜催化方法。易于制备的（亚磷酰胺）-Cu 配合物促进了转化，包括长期稳定的 γ,γ,-二取代烯丙基二硼和苄基亚胺；产品的产率高达 82%，>20:1 dr，>99:1 er。反应通过对映选择性金属转移形成的立体定义的硼稳定烯丙基铜物种进行。1-氨基-3-链烯基硼酸酯产品的实用性通过各种合成转化得到强调。
• Highly enantioselective 1,4-conjugate addition of diethylzinc to acyclic enones with chiral phosphite–pyridine ligands derived from H8-NOBIN
  作者：Yuanchun Hu、Xinmiao Liang、Junwei Wang、Zhuo Zheng、Xinquan Hu

  DOI：10.1016/j.tetasy.2003.09.020

  日期：2003.12

  A series of new phosphite-pyridine ligands, based on the H-8-binaphthyl backbone, were synthesized and employed in the copper-catalyzed enantioselective 1,4-conjugate addition of diethylzinc to acyclic enones. Ligands derived from (S)-H-8-NOBIN provided better results than their parent ligands in the reaction. Ligand L1 provided excellent ees for trans -4-aryl-3-buten-2-ones (up to 97.8% ee) as substrates. Ligand L2 was very efficient for various para-chalcones, and up to 97.2% ee was achieved. (C) 2003 Elsevier Ltd. All rights reserved.
• Chiral Brønsted Acid Catalysts. Activation of Methyl 3,3,3-Trifluoropyruvate by Hydroxymethylpyridine-Containing Half-Sandwich Complexes
  作者：Daniel Carmona、Pilar Lamata、Antonio Sánchez、Pilar Pardo、Ricardo Rodríguez、Paola Ramírez、Fernando J. Lahoz、Pilar García-Orduña、Luis A. Oro

  DOI：10.1021/om5005463

  日期：2014.8.11

  The coordinated OH group in cationic complexes [eta(n)-ring)M(NOH)(Solv)][SbF6] and [(eta(n)-ring)M(NOH)(R)-P1}][SbF6](2) ((eta(n)-ring)M = (eta(5)-C5Me5)Rh, (eta(5)-C5Me5)Ir, (eta(6)-p-MeC(6)H(4)iPr)Ru; NOH = hydroxypyridine ligand; (R)-P1 = (R)-monophos) is deprotonated by Na2CO3, rendering bi- or mononuclear compounds of formulas [(eta(n)-ring)M(kappa N-2,O-mu-O-NO}(2)][SbF6](2) and [(eta(n)-ring)M(NO)(R)-P1}][SbF6], respectively. The complexes have been characterized by analytical and spectroscopic means, including the determination of the crystal structures of [((eta(n)-ring)M(kappa N-2,O-mu-O-NO}(2)[SbF6](2) (NOH = NOH-1, (eta(n)-ring)M = (eta(5)-C5Me5)Rh, 8a; (eta(6)-p-MeC(6)H(4)iPr)Ru, 8c) and [(eta(5)-C5Me5)Ir(NO)-((R)-P1}][SbF6] (NOH = (R)-NOH-2; (R)-11b) by X-ray diffractometric methods. In complexes [(eta(n)-ring)M(NOH)(P*)1[SbF6](2) (P* = chiral phosphoramidite ligand) the proton of the coordinated hydroxypyridine ligand is able to activate the carbonyl group of methyl 3,3,3-trifluoropyruvate toward the Friedel-Crafts addition of indoles. In most cases, quantitative conversion is achieved in a few minutes, at -70 degrees C, with an ee of up to 8296. NMR data support the activation of the pyruvate by interaction between its carbonyl oxygen and the OH group of the coordinated hydroxymethylpyridine. Therefore, the metallic complexes act as Lewis acid assisted Bronsted acid catalysts.
• H8-MonoPhos and its application in catalytic enantioselective hydrogenation of α-dehydroamino acids
  作者：Qingle Zeng、Hui Liu、Aiqiao Mi、Yaozhong Jiang、Xingshu Li、Michael C.K Choi、Albert S.C Chan

  DOI：10.1016/s0040-4020(02)01062-1

  日期：2002.10

  H-8-MonoPhos, a new stable and readily soluble monodentate phosphoramidite ligand, has been facilely prepared from H-8-BINOL. The ligand achieved up to 99.9% ee and 96.7% ee in hydrogenation of dehydroalanine and dehydrohomophenylalanine in a S/C ratio of 500:1, respectively, which are among the best results to date. For dehydrophenylalanine derivatives, it gave good to excellent enantioselectivity. Some factors controlling the enantioselectivity and conversion were examined and are discussed. The interesting effects of ligand/rhodium ratio on the enantioselectivity and conversion were observed, which a mechanism was proposed to explain. (C) 2002 Elsevier Science Ltd. All rights reserved.