CN112375100B - 手性膦氮膦三齿配体、制备方法及其应用 - Google Patents

手性膦氮膦三齿配体、制备方法及其应用 Download PDF

Info

Publication number
CN112375100B
CN112375100B CN202011273102.2A CN202011273102A CN112375100B CN 112375100 B CN112375100 B CN 112375100B CN 202011273102 A CN202011273102 A CN 202011273102A CN 112375100 B CN112375100 B CN 112375100B
Authority
CN
China
Prior art keywords
phosphine
chiral
tridentate ligand
nitrogen
nmr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN202011273102.2A
Other languages
English (en)
Other versions
CN112375100A (zh
Inventor
张俊良
罗文俊
李恒
葛晨宇
杨俊锋
李志铭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fudan University
Zhuhai Fudan Innovation Research Institute
Original Assignee
Fudan University
Zhuhai Fudan Innovation Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fudan University, Zhuhai Fudan Innovation Research Institute filed Critical Fudan University
Priority to CN202011273102.2A priority Critical patent/CN112375100B/zh
Publication of CN112375100A publication Critical patent/CN112375100A/zh
Application granted granted Critical
Publication of CN112375100B publication Critical patent/CN112375100B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
    • C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种手性膦氮膦三齿配体/其制备方法及其应用，属于有机合成领域。本申请提供的手性膦氮膦三齿配体是具有式(I)所示的化合物

Description

手性膦氮膦三齿配体、制备方法及其应用
技术领域
本发明涉及有机合成领域，尤其是一种手性膦氮膦三齿配体、制备方法及其应用。
背景技术
手性在自然界中广泛存在，是自然界的本质属性之一。在生物体内，蛋白质，核苷酸，糖等生物分子绝大数都是手性分子，手性分子往往对生物体进行专一性识别与手性作用，对人类的健康和生存环境有着极其重要的意义。自1961年反应停(沙利度胺)事件，因其强烈致畸作用被全面召回，之后的研究表明，反应停的(R)构型才真正起到镇静作用，而(S)构型具有强烈的致畸作用，这使得手性受到医药和化工界的广泛重视。之后经过研究者们的长时间努力探索，许多手性化合物及其制备的方法被相继开发出来，其中不对称催化合成由于具有手性增值、高对映选择性、经济，易于实现工业化等优点，被认为是理想的构建手性的方法。在2001年，诺贝尔化学奖授予了美国化学家William Knowles博士和BarrySharpless教授以及日本化学家RyojiNoyori教授，以表彰他们对催化不对称合成的重大贡献。
不对称催化的核心问题是设计合成具有高效、高活性以及高选择性的催化剂，而手性配体是手性催化剂产生不对称诱导的源泉。迄今为止，膦配体是研究最多、应用最广泛的配体，现已陆续合成出几千个手性膦配体，以BINAP为代表的手性膦配体的成功，极大地推动了手性膦配体的研究与应用。然而，原料昂贵、合成路线长、产率低、改造难等难题很大程度上制约着手性膦配体的发展。寻找一种原料低廉、环境友好、易于改造、便于高效合成的手性配体的体系具有非常好的应用前景。
发明内容
本发明提供了一种结构简洁，制备方法简单，可改造位点多，具有广阔的应用前景手性膦氮膦三齿配体、制备方法及其应用。
具体地，本发明是通过下述技术方案实现的：
一种手性膦氮膦三齿配体，结构式如式I所示(记为L-Phos)：
式I中，Ar选自
Figure BDA0002778274510000021
或
Figure BDA0002778274510000022
R1、R2分别独立选自C1～C12的烷烃基、C1～C12的烷氧基、
Figure BDA0002778274510000023
Figure BDA0002778274510000024
或
Figure BDA0002778274510000025
R3选自氢、C1～C12的烷烃基、C1～C12的硅氧基、C1～C10的烷酰基、C1～C10的酯基、C1～C10的磺酸酯基、二茂铁基、
Figure BDA0002778274510000026
ORw、SRw；
Rx和Rx’分别独立选自氢、卤素、C1～C12的烷烃基、C1～C10的烷氧基、C1～C10的硅氧基、C1～C10的烷酰基、C1～C10的酯基、C1～C10的磺酸酯基；n选自1～5的整数,；Ry、Rz、Rw分别独立为C1～C10的烷烃基、苯基、取代苯基、杂芳基或苄基；
R4选自氢、C1～C10的烷烃基、C1～C10烷氧基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基上的取代基为C1～C10的烷烃基、烷氧基，取代基数量为1～5，杂芳基为呋喃基、噻吩基或吡啶基；
或R2和R4通过C2～C4的碳链或含氮、氧、硫的碳链链接呈芳香环或杂芳香环。
优选地，手性膦氮膦三齿配体为下述结构式所示化合物中的任意一种：
Figure BDA0002778274510000031
式中Ad为1-金刚烷基。
本发明还提供了一种手性膦氮膦三齿配体的制备方法，用于制备上述的手性膦氮膦三齿配体，反应方程式为：
Figure BDA0002778274510000032
优选地，化合物II参考公开专利(申请号：202010223610.3公开号CN111499666A)和已授权专利(申请号：CN201310671902.3，公开号：CN103709195A)所述的方法，以及其他专利和文章报道(CN103709195A；CN1951945A；Tetrahedron Asymmetry,2015,26,12；ChemCatChem,2015,7,75)的方法得到。
优选地，反应步骤包括：将具有手性的化合物II溶于有机溶剂，加入化合物III，在还原剂的作用下，在一定反应温度下进行一定时间的还原胺化反应，即得。
优选地，所述有机溶剂为甲醇、乙醇、丙醇、异丙醇、丁醇、四氢呋喃、甲苯、二甲苯、甲基叔丁基醚、乙醚、二氧六环、N,N-二甲基甲酰胺、二甲亚砜、二氯甲烷、氯仿、1,2-二氯乙烷的一种或其中几种的混合溶剂。
优选地，所述还原剂为氢化铝锂、硼氢化钠、三乙酰氧基硼氢化钠、氢基硼氢化钠或硼氢化钾中的任意一种或多种。
优选地，所述温度为0℃-100℃。
本发明还提供了手性膦氮膦三齿配体不对称氢化反应中的应用。
优选地，所述不对称氢化反应为芳基酮的不对称氢化反应。
优选地，所述芳基酮的不对称氢化反应的步骤包括：
步骤1，将所述手性膦氮膦三齿配体以及离子型铱化合物在惰性气氛下溶于有机溶剂，得催化剂溶液；
步骤2，将芳基酮溶于所述催化剂溶液，加压环境下反应。
更优选地，所述加压环境为1atm-100atm环境。
具体实施方式
下面结合实施例，对本发明作进一步的详细说明，以下实施例仅仅是用来解释本发明，并不用于限定本发明。
具体地，下述实施例中的原料来源如下：
化合物II-1～II-18均参照公开专利(申请号：202010223610.3公开号CN111499666A)和已授权专利(申请号：CN201310671902.3，公开号：CN103709195A)所述的方法，以及其他专利和文章报道(CN103709195A；CN1951945A；Tetrahedron Asymmetry,2015,26,12；ChemCatChem,2015,7,75)的方法得到。
III-a为商业化试剂CAS号50777-76-9，III-b的CAS号为226089-17-4，参考文献Org.Lett.,2003,5,545进行自制，III-c自制没有CAS号，制备方法如下：
Figure BDA0002778274510000051
III-c的合成：
1)加入对甲苯磺酸，乙二醇，在甲苯中回流，进行醛基保护；2)在正丁基锂，THF，氮气氛围下与氯代环己基膦进行反应；3)进行脱醛基保护得到III-c。
其他试剂均为市售的商业化试剂。
实施例1
配体I-L1的合成
Figure BDA0002778274510000052
在氮气氛围中，在100mL干燥的Schlenk管中加入II-1(0.417g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-a(0.319g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L1(0.320g,46.3％)。
Figure BDA0002778274510000061
1H NMR(400MHz,CDCl3):δ7.72-7.65(m,1H),7.60-7.51(m,4H),7.38-7.20(m,21H),7.18-7.05(m,7H),6.94-6.86(m,2H),5.96(d,J＝8.0Hz,1H),4.05-3.77(m,2H).13CNMR(100MHz,CDCl3):δ148.4,148.2,144.9,144.6,140.4,137.5,137.4,137.1,137.04,137.00,136.5,136.4,136.1,136.0,135.4,135.3,134.03,134.00,133.92,133.91,133.8,133.73,133.71,133.2,132.4,129.8,129.7,129.4,128.9,128.52,128.49,128.46,128.44,128.39,128.36,128.25,128.2,128.12,128.07,128.0,127.6,127.31,127.25,127.0,126.8,126.2,125.4,125.2,63.6,63.3,51.3,51.1.31P NMR(162MHz,CDCl3):δ-15.95,-17.29.
实施例2
配体I-L2的合成
Figure BDA0002778274510000071
在氮气氛围中，在100mL干燥的Schlenk管中加入II-2(0.381g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L2(0.268g,40.1％)。
Figure BDA0002778274510000072
1H NMR(400MHz,CDCl3)：δ7.84(dd,J＝6.4,4.0Hz,1H),7.42(d,J＝2.8Hz,1H),7.38-7.28(m,6H),7.25-7.16(m,8H),7.15-7.06(m,3H),6.92-6.90(m,3H),5.86(d,J＝7.6Hz,1H),3.92(dd,J＝33.6,12.8Hz,2H),2.23(s,3H),1.92-1.72(m,4H),1.75-1.71(m,2H),1.64-1.60(m,4H),1.52-1.47(m,2H),1.31-1.22(m,2H),1.16-1.05(m,5H),1.00-0.83(m,3H).13C NMR(100MHz,CDCl3):δ149.0,148.8,147.5,147.2,140.4,137.7,137.6,136.8,136.7,135.8,135.3,135.2,134.1,133.95,133.86,133.75,133.66,132.69,132.67,129.54,129.49,129.3,128.6,128.5,128.4,128.3,128.2,128.1,128.0,127.9,127.8,126.9,126.1,63.0,62.7,51.1,50.9,34.0,33.89,33.88,33.7,30.6,30.5,30.4,30.3,29.2,29.10,29.06,29.0,27.23,27.18,27.11,27.06,26.99,26.96,26.9,26.3,21.0.31PNMR(162MHz,CDCl3):δ-16.13,-17.50.
实施例3
配体I-L3的合成
Figure BDA0002778274510000082
在氮气氛围中，在100mL干燥的Schlenk管中加入II-3(0.381g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L2(0.246g,36.9％)。
Figure BDA0002778274510000081
1H NMR(400MHz,CDCl3):δ7.84-7.81(m,1H),7.42-7.40(m,1H),7.37-7.25(m,6H),7.24-7.17(m,6H),7.17-7.06(m,4H),7.03-6.97(m,2H),6.94-6.91(m,1H),6.86-6.82(m,1H),5.86(d,J＝8.0Hz,1H),4.00-3.82(m,2H),2.11(s,3H),1.86-1.82(m,3H),1.73-1.70(m,2H),1.61-1.58(m,4H),1.50-1.46(m,2H),1.28-1.24(m,2H),1.15-1.05(m,5H),0.97-0.94(m,2H),0.89-0.83(m,2H).13C NMR(100MHz,CDCl3):δ148.9,148.7,147.5,147.2,143.3,137.9,137.7,137.3,136.8,136.7,135.4,135.3,134.2,134.0,133.85,133.78,133.7,132.75,132.72,129.7,129.6,129.3,128.9,128.5,128.42,128.35,128.33,128.27,128.2,128.1,128.00,127.95,127.8,127.2,126.9,126.2,124.96,124.95,63.1,62.9,51.2,51.0,34.1,34.0,33.9,33.8,30.6,30.5,30.44,30.38,29.2,29.14,29.08,29.0,27.24,27.19,27.12,27.08,27.07,27.04,27.01,26.96,26.9,26.3,21.3.31P NMR(162MHz,CDCl3):δ-16.14,-17.78.
实施例4
配体I-L4的合成
Figure BDA0002778274510000091
在氮气氛围中，在100mL干燥的Schlenk管中加入II-4(0.381g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L4(0.206g,30.9％)。
Figure BDA0002778274510000092
1H NMR(400MHz,CDCl3):δ7.70-7.65(m,1H),7.38-7.25(m,8H),7.22-7.12(m,7H),7.08-6.93(m,6H),5.91(d,J＝6.8Hz,1H),4.04-3.92(m,2H),2.17(s,3H),1.87-1.82(m,4H),1.74-1.70(m,3H),1.60-1.58(m,3H),1.28-1.24(m,3H),1.13-1.06(m,5H),0.97-0.93(m,2H),0.90-0.83(m,2H).13C NMR(100MHz,CDCl3):δ148.00,147.7,147.3,147.1,140.8,137.7,137.5,136.5,136.4,136.3,136.2,136.0,134.5,133.8,133.73,133.70,133.6,133.54,133.50,132.49,132.46,130.2,129.21,129.16,129.1,128.49,128.47,128.40,128.35,128.2,128.1,128.0,127.0,126.5,126.0,125.5,60.8,60.6,51.5,51.2,33.91,33.86,33.8,33.7,30.6,30.5,30.4,30.3,29.2,29.10,29.0,28.9,27.22,27.16,27.10,27.06,27.04,26.99,26.91,26.88,26.4,26.3,19.49,19.47,19.44,19.42.31P NMR(162MHz,CDCl3):δ-16.44,-17.50.
实施例5
配体I-L5的合成
Figure BDA0002778274510000101
在氮气氛围中，在100mL干燥的Schlenk管中加入II-5(0.401g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L5(0.380g,55.3％)。
Figure BDA0002778274510000102
1H NMR(400MHz,CDCl3):δ7.80(dd,J＝7.2,4.4Hz,1H),7.45-7.38(m,1H),7.38-7.33(m,1H),7.33-7.28(m,3H),7.29-7.23(m,4H),7.22-7.16(m,6H),7.15-7.10(m,1H),7.08-7.00(m,4H),6.94-6.88(m,1H),5.82(d,J＝8.0Hz,1H),3.89(dd,J＝29.2,12.8Hz,2H),1.90-1.79(m,4H),1.74-1.68(m,2H),1.64-1.56(m,4H),1.50-1.42(m,2H),1.28-1.20(m,2H),1.17-1.02(m,6H),0.95-0.86(m,2H).13C NMR(100MHz,CDCl3):δ148.2,148.0,147.2,146.9,141.9,137.4,137.3,136.3,136.2,135.4,135.30,134.25,134.0,133.9133.8,133.7,132.84,132.81,132.1,129.6,129.5,129.4,128.6,128.5,128.4,128.37,128.33,128.26,128.0,127.74,127.69,127.2,126.3,62.6,62.3,51.2,51.0,34.0,33.9,33.8,30.58,30.55,30.41,30.38,29.2,29.13,29.09,29.0,27.22,27.17,27.1,27.05,26.98,26.95,26.89,26.3.31P NMR(162MHz,CDCl3):δ-16.10,-17.70.
实施例6
配体I-L6的合成
Figure BDA0002778274510000111
在氮气氛围中，在100mL干燥的Schlenk管中加入II-6(0.443g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L6(0.425g,58.2％)。
Figure BDA0002778274510000121
1H NMR(400MHz,CDCl3):δ7.82(s,1H),7.42-7.18(m,17H),7.15-7.03(m,6H),7.02-6.95(m,2H),6.86(s,1H),5.84(d,J＝7.6Hz,1H),3.87(dd,J＝29.6,12.8Hz,2H),1.78-1.72(m,4H),1.64-1.60(m,2H),1.56-1.48(m,4H),1.42-1.40(m,2H),1.21-1.11(m,3H),1.06-0.96(m,4H),0.88-0.70(m,3H).13C NMR(100MHz,CDCl3):δ148.7,148.42,147.38,147.1,142.5,141.2,139.2,137.7,137.6,136.6,136.5,135.5,135.3,134.3,133.93,133.86,133.73,133.67,132.8,132.7,129.62,129.56,129.4,128.6,128.5,128.44,128.38,128.2,128.1,127.9,127.8,127.02,126.95,126.8,126.6,126.2,63.0,62.7,51.2,51.0,34.0,33.9,33.8,30.6,30.5,30.40,30.38,29.2,29.1,29.0,27.21,27.17,27.09,27.05,27.0,26.95,26.87,26.3.31P NMR(162MHz,CDCl3):δ-16.09,-17.66.
实施例7
配体I-L7的合成
Figure BDA0002778274510000122
在氮气氛围中，在100mL干燥的Schlenk管中加入II-7(0.417g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L7(0.290g,41.3％)。
Figure BDA0002778274510000131
1H NMR(400MHz,CDCl3):δ7.85(d,J＝8.8Hz,1H),7.72(d,J＝8.0Hz,1H),7.64-7.58(m,3H),7.41-7.33(m,2H),7.33-7.27(m,7H),7.24-7.17(m,5H),7.16-7.11(m,3H),7.10-7.03(m,3H),6.59(d,J＝7.2Hz,1H),4.11(dd,J＝41.2,12.4Hz,2H),1.83-1.78(m,4H),1.70-1.68(m,2H),1.58-1.50m,4H),1.26-1.16(m,3H),1.15-1.00(m,6H),0.88-0.82(m,3H).13C NMR(100MHz,CDCl3):δ148.2,147.9,147.4,147.1,138.2,137.6,137.5,136.2,136.1,136.0,134.5,134.1,133.93,133.90,133.82,133.75,133.6,132.6,131.5,129.3,129.25,129.21,128.58,128.55,128.48,128.46,128.4,128.14,128.07,127.4,127.2,126.2,126.1,125.7,125.2,125.0,124.18,124.16,60.2,60.0,51.7,51.5,33.9,33.8,30.6,30.5,30.4,30.3,29.14,29.06,29.0,27.3,27.2,27.13,27.08,27.04,27.00,26.96,26.9,26.4.31P NMR(162MHz,CDCl3):δ-16.51,-18.01.
实施例8
配体I-L8的合成
Figure BDA0002778274510000132
在氮气氛围中，在100mL干燥的Schlenk管中加入II-8(0.425g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L8(0.150g,21.1％)。
Figure BDA0002778274510000141
1H NMR(400MHz,CDCl3):δ7.72(dd,J＝7.2,4.4Hz,1H),7.44-7.34(m,2H),7.33-7.22(m,10H),7.21-7.13(m,3H),7.12-7.08(m,2H),4.71(d,J＝8.8Hz,1H),3.34(dd,J＝80.8,11.6Hz,2H),1.92-1.80(m,8H),1.79-1.67(m,5H),1.65-1.49(m,15H),1.20-1.08(m,5H),1.05-0.99(m,1H),0.97-0.83(m,3H).13C NMR(100MHz,CDCl3):δ148.2,148.0,147.7,147.5,138.1,138.0,137.7,137.5,134.70,134.69,134.0,133.82,133.76,133.6,133.4,132.63,132.61,129.82,129.76,129.0,128.9,128.52,128.46,128.3,128.2,128.0,127.2,126.46,126.0,124.4,123.9,119.1,72.9,68.7,68.5,51.7,51.5,39.5,39.4,37.9,37.1,36.4,34.4,34.3,33.6,33.5,31.4,30.7,30.6,30.53,30.48,30.4,30.2,29.5,29.4,28.9,28.9,28.7,28.6,27.3,27.2,27.14,27.05,27.0,26.9,26.5,26.4.31P NMR(162MHz,CDCl3):δ-15.80,-17.61.
实施例9
配体I-L9的合成
Figure BDA0002778274510000142
在氮气氛围中，在100mL干燥的Schlenk管中加入II-9(0.475g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.166g，1.1mmol)和冰醋酸(37μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.189g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L9(0.110g,28.6％)。
Figure BDA0002778274510000151
1H NMR(400MHz,CDCl3):δ7.76(dd,J＝7.6,4.4Hz,1H),7.40(d,J＝7.2Hz,1H),7.36-7.28(m,11H),7.28-7.24(s,2H),7.24-7.19(m,1H),7.24-7.18(m,1H),6.92(dd,J＝7.6,4.0Hz,1H),5.73(d,J＝8.8Hz,1H),4.34(s,1H),4.14(s,5H),4.03(d,J＝19.2Hz,1H),3.98(s,1H),3.94-3.86(m,2H),3.49(d,J＝12.4Hz,1H),2.02-1.96(m,1H),1.89-1.75(m,4H),1.68-1.54(m,7H),1.22-1.15(m,3H),1.13-1.04(m,2H),1.03-0.93(m,3H),0.89-0.77(m,2H).13C NMR(100MHz,CDCl3):δ150.2,150.0,147.9,147.7,137.6,137.5,137.3,137.1,135.2,135.1,134.2,134.1,134.0,133.93,133.90,133.73,133.65,133.5,133.2,132.50,132.47,129.9,129.8,129.5,128.6,128.47,128.45,128.41,128.39,127.84,127.78,126.9,126.1,94.32,68.64,68.62,67.3,67.2,67.1,66.7,65.7,58.5,58.3,50.6,50.4,34.5,34.3,33.1,33.0,31.5,30.7,30.6,30.3,30.2,30.1,29.5,29.4,28.6,28.5,27.5,27.3,27.23,27.17,27.1,27.0,26.9,26.42,26.36.31P NMR(162MHz,CDCl3):δ-16.30,-18.42.
实施例10
配体I-L10的合成
Figure BDA0002778274510000161
在氮气氛围中，在100mL干燥的Schlenk管中加入II-10(0.437g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L10(0.540g,74.7％)。
Figure BDA0002778274510000162
1H NMR(400MHz,CDCl3):δ7.59(s,1H),7.44(s,1H),7.40-7.30(m,2H),7.28-7.19(m,7H),7.18-7.12(m,5H),7.08-7.02(m,4H),6.89(d,J＝8.0Hz,1H),5.95(d,J＝6.7Hz,1H),4.02-3.92(m,2H),2.10(s,3H),1.84-1.80(m,3H),1.77-1.67(m,3H),1.62-1.45(m,6H),1.39-1.25(m,3H),1.21(s,9H),1.14-1.04(m,5H),0.94-0.83(m,2H).13C NMR(100MHz,CDCl3):δ148.3,148.1,147.5,147.2,140.1,137.7,137.6,136.8,136.7,136.1,136.0,134.5,133.7,133.5,133.3,132.4,129.8,129.3,129.2,129.1,128.5,128.4,128.35,128.28,128.2,128.1,128.0,126.9,125.9,125.2,123.1,61.3,61.0,51.6,51.4,34.4,34.0,33.8,31.43,30.6,30.5,30.4,30.3,29.1,29.0,28.9,27.2,27.1,27.02,26.95,26.3,18.92,18.89.31P NMR(162MHz,CDCl3):δ-16.92,-17.97.
实施例11
配体I-L11的合成
Figure BDA0002778274510000171
在氮气氛围中，在100mL干燥的Schlenk管中加入II-11(0.479g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L11(0.450g,58.8％)。
Figure BDA0002778274510000172
1H NMR(400MHz,CDCl3):δ7.81(s,1H),7.40(s,1H),7.37-7.17(m,14H),7.14-7.08(m,4H),6.94(s,1H),5.99(d,J＝8.0Hz,1H),3.93(dd,J＝44.8,12.4Hz,2H),1.84(s,4H),1.74-1.68(m,2H),1.60-1.56(m,4H),1.50-1.45(m,2H),1.31(d,J＝22.5Hz,2H),1.19(s,18H),1.10-1.08(m,5H),1.00-0.83(m,3H).13C NMR(100MHz,CDCl3):δ150.1,149.7,149.5,147.8,147.5,142.6,138.3,138.2,137.1,137.0,135.2,135.1,134.3,134.0,133.8,133.7,133.6,133.5,132.7,129.74,129.68,129.4,128.5,128.4,128.31,128.26,128.2,128.1,128.0,127.99,126.8,126.1,122.1,120.3,63.9,63.7,51.5,51.3,34.7,34.1,34.0,33.8,31.5,30.6,30.50,30.45,30.3,29.2,29.1,29.0,28.9,27.3,27.24,27.15,27.12,27.05,27.0,26.3.31P NMR(162MHz,CDCl3):δ-16.32,-18.17.
实施例12
配体I-L12的合成
Figure BDA0002778274510000181
在氮气氛围中，在100mL干燥的Schlenk管中加入II-12(0.519g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L12(0.480g,59.6％)。
Figure BDA0002778274510000182
1H NMR(400MHz,CDCl3):δ7.91(dd,J＝7.2,4.0Hz,1H),7.53(d,J＝1.6Hz,2H),7.47(d,J＝1.6Hz,2H),7.46-7.44(m,3H),7.43-7.40(m,1H),7.41-7.35(m,5H),7.34-7.28(m,5H),7.28-7.21(m,5H),7.17-7.06(m,6H),6.98-6.92(m,1H),6.08(d,J＝8.4Hz,1H),4.15-3.90(m,2H),1.89-1.78(m,4H),1.74-1.61(m,3H),1.55-1.42(m,5H),1.25-1.15(m,2H),1.13-1.01(m,5H),0.93-0.82(m,3H).13C NMR(100MHz,CDCl3):δ148.8,148.5,147.5,147.2,144.5,141.3,138.0,137.9,136.4,136.3,135.4,135.3,134.4,134.2,134.0,133.9,133.8,133.7,133.6,132.9,132.8,129.83,129.77,129.5,128.6,128.5,128.44,128.36,128.23,128.17,128.04,127.98,127.3,127.1,127.0,126.3,126.1,124.3,63.5,63.2,51.6,51.4,34.2,34.1,34.0,33.9,30.7,30.5,30.5,30.4,29.3,29.2,29.1,29.0,27.3,27.2,27.13,27.07,27.00,26.96,26.9,26.31,26.29.31P NMR(162MHz,CDCl3):δ-16.08,-18.08.
实施例13
配体I-L13的合成
Figure BDA0002778274510000191
在氮气氛围中，在100mL干燥的Schlenk管中加入II-13(0.503g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L13(0.460g,58.3％)。
Figure BDA0002778274510000192
1H NMR(400MHz,CDCl3):δ8.42(s,1H),7.73(d,J＝8.0Hz,1H),7.59(d,J＝8.4Hz,1H),7.32(d,J＝7.6Hz,1H),7.26-7.20(m,9H),7.21-7.16(m,3H),7.15-7.08(m,2H),7.06-7.00(m,2H),6.92(dd,J＝7.2,3.6Hz,1H),6.49(d,J＝8.0Hz,1H),4.10-3.82(m,2H),1.88-1.68(m,7H),1.66-1.54(m,5H),1.27-1.19(m,2H),1.17-1.07(m,4H),1.06-0.98(m,2H),0.92-0.83(m,2H).13C NMR(100MHz,CDCl3):δ147.4,147.1,146.5,146.3,142.4,137.4,137.3,137.1,137.0,136.5,136.3,135.68,135.66,133.9,133.72,133.66,133.6,133.5,133.4,132.35,132.32,129.2,129.04,128.98,128.52,128.46,128.40,128.3,128.2,128.0,127.83,127.77,127.6,127.01,126.95,126.02,125.51,125.03,124.99,124.10,124.06,122.30,119.6,60.8,60.6,51.4,51.2,34.2,34.0,33.6,33.5,30.5,30.35,30.30,30.2,30.1,29.1,29.0,28.7,28.6,27.3,27.21,27.16,27.1,27.05,26.97,26.9,26.3.19FNMR(377MHz,CDCl3):δ19F NMR(377MHz,CDCl3):δ-59.23,-62.59.31P NMR(162MHz,CDCl3):δ-16.46,-18.49.
实施例14
配体I-L14的合成
Figure BDA0002778274510000201
在氮气氛围中，在100mL干燥的Schlenk管中加入II-14(0.477g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L14(0.330g,43.3％)。
Figure BDA0002778274510000211
1H NMR(400MHz,CDCl3):δ7.88(dd,J＝7.2,4.4Hz,1H),7.43-7.38(m,1H),7.36(d,J＝6.8Hz,1H),7.33-7.26(m,7H),7.25-7.17(m,4H),7.16-7.09(m,2H),7.06-6.97(m,4H),6.97-6.91(m,1H),5.88(d,J＝8.0Hz,1H),4.02-3.79(m,2H),1.82(d,J＝9.6Hz,4H),1.71(d,J＝13.2Hz,3H),1.62-1.55(m,9H),1.50-1.56(m,2H),1.27-1.20(m,4H),1.16(s,6H),1.15(s,3H),1.08(s,3H),0.98-0.82(m,4H).13C NMR(100MHz,CDCl3):δ149.3,149.1,147.7,147.4,144.1,142.6,140.3,138.2,138.0,137.0,136.9,135.34,135.2,134.34,134.33,134.0,133.9,133.8,133.72,133.66,133.5,132.69,132.66,129.71,129.65,129.3,128.5,128.4,128.32,128.27,128.2,128.1,127.9,127.8,126.8,126.1,126.0,125.2,63.4,63.1,51.3,51.1,35.2,35.1,34.13,34.09,34.0,33.91,33.87,33.8,31.9,31.85,31.79,31.7,30.6,30.5,30.42,30.35,29.2,29.1,29.05,28.97,27.3,27.23,27.15,27.11,27.06,27.04,26.98,26.90,26.4.31P NMR(162MHz,CDCl3):δ-16.25,-18.15.
实施例15
配体I-L15的合成
Figure BDA0002778274510000212
在氮气氛围中，在100mL干燥的Schlenk管中加入II-15(0.409g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L15(0.270g,38.8％)。
Figure BDA0002778274510000221
1H NMR(400MHz,CDCl3):δ8.05(s,1H),7.39-7.34(m,3H),7.22-7.20(m,5H),7.18-7.12(m,2H),7.10-7.02(m,5H),6.88(t,J＝7.6Hz,2H),6.37(s,2H),5.81(s,1H),4.27-4.09(m,2H),2.05(s,6H),2.00(s,3H),1.85-1.83(m,4H),1.77-1.68(m,3H),1.59-1.57(m,4H),1.28-1.24(m,2H),1.14-1.08(m,5H),0.98-0.91(m,2H),0.89-0.84(m,2H).13C NMR(100MHz,CDCl3):δ148.6,148.4,147.5,147.3,139.5,139.4,137.4,136.8,136.1,135.6,135.4,133.8,133.6,133.4,133.22,133.15,133.0,132.64,132.61,129.7,129.14,129.08,129.0,128.9,128.5,128.3,128.15,128.09,127.7,127.6,127.5,127.4,126.3,126.0,61.2,61.0,51.5,51.3,34.0,33.8,33.7,30.6,30.4,29.13,29.06,29.0,27.22,27.18,27.10,27.06,27.01,26.99,26.93,26.89,26.3,21.5,21.5,20.6.31P NMR(162MHz,CDCl3):δ-16.36,-17.15.
实施例16
配体I-L16的合成
Figure BDA0002778274510000231
在氮气氛围中，在100mL干燥的Schlenk管中加入II-16(0.457g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L16(0.428g,57.6％)。
Figure BDA0002778274510000232
1H NMR(400MHz,CDCl3):δ8.00-7.92(m,1H),7.48-7.37(m,2H),7.30-7.26(m,4H),7.25-7.19(m,4H),7.19-7.11(m,4H),6.98-6.90(m,3H),6.08(d,J＝5.6Hz,1H),4.03(s,2H),1.92-1.69(m,6H),1.60-1.58(m,4H),1.28-1.00(m,9H),0.95-0.78(m,3H).13C NMR(100MHz,CDCl3):δ146.2,145.9,145.0,144.7,143.8,137.4,137.3,135.4,135.3,134.9,134.8,134.6,134.1,133.7,133.5,133.2,133.0,132.81,132.79,130.0,129.9,129.0,128.8,128.4,128.4,128.0,127.9,127.5,126.7,54.4,54.2,50.9,50.7,34.00,33.9,33.6,33.5,30.6,30.5,30.3,29.2,29.1,29.0,28.9,27.13,27.08,27.0,26.9,26.31,26.29.19F NMR(377MHz,CDCl3):δ-139.95,-156.85,-163.01.31P NMR(162MHz,CDCl3):δ-15.79,-17.99.
实施例17
配体I-L17的合成
Figure BDA0002778274510000241
在氮气氛围中，在100mL干燥的Schlenk管中加入II-17(0.501g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-b(0.332g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L17(0.328g,41.7％)。
Figure BDA0002778274510000242
1H NMR(400MHz,CDCl3):δ7.58-7.55(m,1H),7.43-7.4(m,1H),7.30-7.23(m,6H),7.22-7.10(m,5H),6.98-6.93(m,2H),6.39(d,J＝3.2Hz,1H),5.95(dd,J＝9.6,1.6Hz,2H),4.08-4.36(m,2H),1.91-1.68(m,7H),1.64-1.52(m,5H),1.17-1.02(m,6H),0.94-0.80(m,4H).13C NMR(100MHz,CDCl3):δ148.8,147.0,146.2,145.9,140.3,140.0,137.6,137.5,135.6,135.5,133.5,133.3,133.0,132.90,132.87,132.8,130.0,129.9,129.3,128.8,128.5,128.4,128.3,128.02,127.95,127.2,127.1,126.7,113.9,108.7,108.6,101.2,54.1,53.8,50.9,50.7,33.9,33.8,33.7,33.6,30.6,30.5,30.4,30.3,29.2,29.1,29.0,27.1,37.98,26.0,26.32,26.30.19F NMR(377MHz,CDCl3):δ-139.91,-156.98,-163.05.31PNMR(162MHz,CDCl3):δ-15.86,-17.72.
实施例18
配体I-L18的合成
Figure BDA0002778274510000251
在氮气氛围中，在100mL干燥的Schlenk管中加入II-18(0.381g,1.0mmol)干燥的，之后注射器加入30ml无水甲醇，搅拌溶解。加入III-c(0.396g，1.1mmol)和冰醋酸(74μL)室温下搅拌反应3个小时，打开反口筛，一次性倒入NaBH3CN(0.377g,6.0mmol)，反应在40℃下反应12小时。反应结束，体系旋干，加入二氯甲烷溶解，饱和碳酸氢钠溶液淬灭。二氯甲烷萃取，合并有机相，有机相用无水硫酸钠干燥，抽滤除去干燥剂，滤液用旋蒸回收溶剂。经柱层析(石油醚：乙酸乙酯＝20:1)得到白色固体I-L17(0.280g,35.0％)。
Figure BDA0002778274510000252
1H NMR(400MHz,CDCl3):δ8.06-7.99(m,1H),7.43-7.37(m,1H),7.31-7.22(m,8H),7.19-7.06(m,6H),7.00-6.91(m,3H),6.77(dd,J＝7.2,3.6Hz,1H),6.65(d,J＝8.4Hz,1H),5.91(d,J＝8.0Hz,1H),4.63-4.56(m,1H),3.92-3.80(m,2H),3.52(s,3H),1.89-1.87(m,2H),1.72-1.68(m,3H),1.58-1.48(m,4H),1.27(s,6H),1.24-1.16(m,5H),1.13-1.02(m,4H),0.98-0.93(m,1H),0.90-0.82(m,3H).13C NMR(100MHz,CDCl3):δ160.0,159.9,157.8,150.4,150.1,149.9,149.7,142.5,138.6,138.5,137.6,137.1,137.0,135.1,135.0,134.6,133.8,133.6,133.4,133.2,130.0,129.3,128.33,128.27,128.2,128.1,128.0,127.9,127.7,127.6,126.7,126.41,126.39,122.8,122.6,122.0,121.9,109.1,68.2,64.0,63.5,63.2,52.4,52.1,35.6,34.9,34.84,34.81,34.7,33.1,32.8,32.3,32.1,30.7,30.6,30.5,27.4,27.35,27.27,27.23,27.20,27.09,27.06,26.9,26.4,26.3.31P NMR(162MHz,CDCl3):δ-9.12,-18.75.
实施例19
苯乙酮的不对称氢化反应
Figure BDA0002778274510000261
(1)将配体I-L12(20.1mg,0.024mmol)，金属[Ir(COD)Cl]2(8.0mg,0.011mmol),加入反应瓶中，氩气氛围下加入异丙醇(2.5ml),25℃下搅拌反应0.5h，制得催化剂溶液；
(2)在高压釜中加入苯乙酮(120mg，1mmol)，叔丁醇锂(4mg，0.05mmol)，异丙醇(4mL),加入步骤(1)所制备的催化剂溶液，充入H2(3.0MPa)，室温下反应12h。反应完毕后释放氢气，反应液经硅藻土过滤得120mg产物1-苯乙醇，收率99％，ee值47％。

Claims (10)

1.一种手性膦氮膦三齿配体，其特征在于，结构式如式I所示：
Figure FDA0003349573510000011
式I中，Ar选自
Figure FDA0003349573510000012
R1、R2分别独立选自C1～C12的烷烃基、C1～C12的烷氧基或
Figure FDA0003349573510000013
R3选自C1～C12的烷烃基、二茂铁基、
Figure FDA0003349573510000014
Rx和Rx’分别独立选自氢、卤素、C1～C12的烷烃基、C1～C10的烷氧基、C1～C10的硅氧基、C1～C10的烷酰基、C1～C10的酯基、C1～C10的磺酸酯基；
R4选自氢、C1～C10的烷烃基、C1～C10烷氧基、苯基、取代苯基、1-萘基、2-萘基、杂芳基或苄基，所述取代苯基上的取代基为C1～C10的烷烃基、C1～C10的烷氧基，取代基数量为1～5，杂芳基为呋喃基、噻吩基或吡啶基。
2.根据权利要求1所述的手性膦氮膦三齿配体，其特征在于，为下述结构式所示化合物中的任意一种：
Figure FDA0003349573510000021
3.一种手性膦氮膦三齿配体的制备方法，用于制备权利要求1或2所述的手性膦氮膦三齿配体，其特征在于，
反应方程式为：
Figure FDA0003349573510000022
4.根据权利要求3所述的手性膦氮膦三齿配体的制备方法，其特征在于，反应步骤包括：将具有手性的化合物II溶于有机溶剂，加入化合物III，在还原剂的作用下，在一定反应温度下进行一定时间的还原胺化反应，即得。
5.根据权利要求4所述的手性膦氮膦三齿配体的制备方法，其特征在于，
其中，所述有机溶剂为甲醇、乙醇、丙醇、异丙醇、丁醇、四氢呋喃、甲苯、二甲苯、甲基叔丁基醚、乙醚、二氧六环、N,N-二甲基甲酰胺、二甲亚砜、二氯甲烷、氯仿、1,2-二氯乙烷的一种或其中几种的混合溶剂。
6.根据权利要求4所述的手性膦氮膦三齿配体的制备方法，其特征在于，
其中，所述还原剂为氢化铝锂、硼氢化钠、三乙酰氧基硼氢化钠、氢基硼氢化钠或硼氢化钾中的任意一种或多种。
7.根据权利要求4所述的手性膦氮膦三齿配体的制备方法，其特征在于，
其中，所述温度为0℃-100℃。
8.权利要求1或2所述的手性膦氮膦三齿配体不对称氢化反应中的应用。
9.根据权利要求8所述的应用，其特征在于，所述不对称氢化反应为芳基酮的不对称氢化反应。
10.根据权利要求9所述的应用，其特征在于，所述芳基酮的不对称氢化反应的步骤包括：
步骤1，将所述手性膦氮膦三齿配体以及离子型铱化合物在惰性气氛下溶于有机溶剂，得催化剂溶液；
步骤2，将芳基酮溶于所述催化剂溶液，加压环境下反应，即得手性仲醇。
CN202011273102.2A 2020-11-13 2020-11-13 手性膦氮膦三齿配体、制备方法及其应用 Expired - Fee Related CN112375100B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011273102.2A CN112375100B (zh) 2020-11-13 2020-11-13 手性膦氮膦三齿配体、制备方法及其应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011273102.2A CN112375100B (zh) 2020-11-13 2020-11-13 手性膦氮膦三齿配体、制备方法及其应用

Publications (2)

Publication Number Publication Date
CN112375100A CN112375100A (zh) 2021-02-19
CN112375100B true CN112375100B (zh) 2021-12-21

Family

ID=74583971

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011273102.2A Expired - Fee Related CN112375100B (zh) 2020-11-13 2020-11-13 手性膦氮膦三齿配体、制备方法及其应用

Country Status (1)

Country Link
CN (1) CN112375100B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113912474A (zh) * 2021-11-09 2022-01-11 珠海复旦创新研究院 一种手性叔醇的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109776245A (zh) * 2017-11-14 2019-05-21 中国科学院大连化学物理研究所 一种铱催化不对称氢化制备手性醇的方法
CN111484533A (zh) * 2020-01-09 2020-08-04 南开大学 手性螺环膦-氮-膦三齿配体及其铱催化剂的制备方法和应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109776245A (zh) * 2017-11-14 2019-05-21 中国科学院大连化学物理研究所 一种铱催化不对称氢化制备手性醇的方法
CN111484533A (zh) * 2020-01-09 2020-08-04 南开大学 手性螺环膦-氮-膦三齿配体及其铱催化剂的制备方法和应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Benzylene-linked [PNP] scaffolds and their cyclometalated zirconium and hafnium complexes;Malte Sietzen et al.;《Dalton Transactions》;20171231;第5816-5834页 *
Highly efficient hydrogenation of carbon dioxide to formate catalyzed by iridium(III) complexes of imine-diphosphine ligands;Liu, Chong et al.;《Chemical Science》;20151231;第2928-2931页 *
Selective hydrogenation of nitriles to primary amines catalyzed by a novel iron complex;Chakraborty, Subrata et al.;《Chemical Communications》;20161231;第1812-1815页 *

Also Published As

Publication number Publication date
CN112375100A (zh) 2021-02-19

Similar Documents

Publication Publication Date Title
CN112375100B (zh) 手性膦氮膦三齿配体、制备方法及其应用
CN109134875B (zh) L-薄荷醇为手性源的手性共价有机骨架材料的制备
CN104379558A (zh) 利用谷氨酸衍生物和羟基苯胺或羟基被保护的羟基苯胺合成拉马琳以及拉马琳前体的方法
An et al. Isosteviol‐amino Acid Conjugates as Highly Efficient Organocatalysts for the Asymmetric One‐pot Three‐component Mannich Reactions
CN114716361B (zh) 一种合成手性螺环茚酮-吡咯类化合物的方法
CN112264105B (zh) 一种用于取代酮和双酚f合成的负载型钯催化剂
CN101486737B (zh) 含季胺盐基团的二茂铁膦亚胺配体、其制备以及在催化不对称烯丙基取代反应中的应用
CN110105274B (zh) 一种3-(2-氨基芳基)喹啉类化合物的合成方法
CN114213465B (zh) 具有拆分功能的Ir(Ⅲ)基手性金属-有机多孔材料及制备方法和应用
CN113121350B (zh) 动态动力学拆分α-芳基-α-烷基羧酸酯的方法及应用
Jin et al. Pd-catalyzed asymmetric carbonyl alkynylation: Synthesis of axial chiral ynones
CN112851708B (zh) 催化端炔或端位共轭烯炔制备烯醛的方法及其使用的双膦配体
CN114573473B (zh) 一种(R)-α-芳基丙氨酸酯衍生物的制备方法
Wang et al. Photoenolization/nucleophilic addition enables direct access to 3-alkyl-3-hydroxy-indolin-2-ones
CN111943874A (zh) 一种芳基萘普生衍生物高价碘化合物及其制备方法和应用
WO2019119516A1 (zh) 基于四甲基螺二氢茚骨架的双噁唑啉配体化合物及其中间体和制备方法与用途
CN116836107B (zh) 一种咔唑并八元环大共轭结构oled材料及制备方法
CN101142164B (zh) 生产光学活性3-苯基丙酸衍生物以及后者的后续产物的生产方法
CN112430212B (zh) 可循环铋络合物催化的不对称n-二芳基甲基取代的杂环化合物的合成方法
CN112574164B (zh) 基于手性联萘酚合成手性螺环分子的方法
CN109851634B (zh) 手性单膦配体Yu-Phos及其全构型的制备方法和应用
CN114213370B (zh) 一种光诱导nhpi酯脱羧偶联合成烷基化富电子杂环芳烃方法
CN113929714B (zh) 一种手性苄基硅烷类化合物的制备方法
CN111807942B (zh) 一种多取代茚酮衍生物的制备方法
CN116675629A (zh) 一种基于天然氨基酸的手性双羧酸四齿双核铑催化剂、合成方法及其应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20211221