CN109232650B - Chiral 1-phospha norbornadiene derivatives and synthetic methods thereof - Google Patents
Chiral 1-phospha norbornadiene derivatives and synthetic methods thereof Download PDFInfo
- Publication number
- CN109232650B CN109232650B CN201811293427.XA CN201811293427A CN109232650B CN 109232650 B CN109232650 B CN 109232650B CN 201811293427 A CN201811293427 A CN 201811293427A CN 109232650 B CN109232650 B CN 109232650B
- Authority
- CN
- China
- Prior art keywords
- compound
- reaction
- ppm
- cdcl
- 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
Links
- OIFRCRAYWOPACM-UHFFFAOYSA-N 1-phosphabicyclo[2.2.1]hepta-2,4-diene Chemical class C1P2CC=C1C=C2 OIFRCRAYWOPACM-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000010189 synthetic method Methods 0.000 title description 3
- -1 1-phospha norbornadiene compound Chemical class 0.000 claims abstract description 9
- 238000001308 synthesis method Methods 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- DJMUYABFXCIYSC-UHFFFAOYSA-N 1H-phosphole Chemical compound C=1C=CPC=1 DJMUYABFXCIYSC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- IDASOVSVRKONFS-UHFFFAOYSA-N 3-phenylprop-2-ynal Chemical compound O=CC#CC1=CC=CC=C1 IDASOVSVRKONFS-UHFFFAOYSA-N 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 238000004296 chiral HPLC Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- LFILDSDQMSCNBV-LURJTMIESA-N propane-2-sulfinamide Chemical compound CC(C)[S@@](N)=O LFILDSDQMSCNBV-LURJTMIESA-N 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- HSYLTRBDKXZSGS-UHFFFAOYSA-N silver;bis(trifluoromethylsulfonyl)azanide Chemical compound [Ag+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HSYLTRBDKXZSGS-UHFFFAOYSA-N 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Description
技术领域technical field
本发明属于有机化学合成领域，具体涉及在不对称催化领域应用的1-磷杂降冰片二烯类化合物及其合成方法。The invention belongs to the field of organic chemical synthesis, in particular to a 1-phospha norbornadiene compound used in the field of asymmetric catalysis and a synthesis method thereof.
背景技术Background technique
在不对称催化领域，手性有机磷化物是重要的配体或者催化剂。由于拥有一对孤对电子，三价有机磷化物既可以作为配体与金属络合，生成金属络合物，参与金属催化的不对称反应，又可以作为催化剂，进攻缺电子烯烃生成碳负离子中间体，进而催化化学反应。在之前的研究中，化学家们把关注点集中在与磷相连的手性骨架的选择，也就是说，目标产物的手性是通过手性骨架的诱导产生的。因为磷本身的性质导致了磷手性中心难以合成而且高温下易于外消旋化，所以造成磷手性中心配体的研究非常少。In the field of asymmetric catalysis, chiral organophosphides are important ligands or catalysts. Due to the possession of a lone pair of electrons, trivalent organophosphides can be used as ligands to complex with metals to form metal complexes and participate in metal-catalyzed asymmetric reactions, and can also be used as catalysts to attack electron-deficient alkenes to generate carbanion intermediates body to catalyze chemical reactions. In previous studies, chemists have focused on the selection of chiral backbones linked to phosphorus, that is, the chirality of the target product is induced by the chiral backbone. Because the nature of phosphorus itself makes phosphorus chiral centers difficult to synthesize and easy to racemize at high temperatures, there are very few studies on the ligands of phosphorus chiral centers.
到目前为止，将磷原子嵌入到刚性骨架中设计出具有磷手性中心手性磷-氧配体仍然未见报道。So far, the design of chiral phosphorus-oxygen ligands with phosphorus chiral centers by intercalating phosphorus atoms into rigid frameworks has not been reported.
发明内容SUMMARY OF THE INVENTION
针对目前的技术现状，本发明目的在于提供一种新型的1-磷杂降冰片二烯类手性磷-氧配体；另一目的在于提供其合成方法。In view of the current state of the art, the purpose of the present invention is to provide a novel 1-phosphanorbornadiene chiral phosphorus-oxygen ligand; another purpose is to provide a synthesis method thereof.
为实现本发明目的，本发明以磷杂环戊二烯类化合物为起始物，通过磷杂D-A反应生成1-磷杂降冰片二烯类化合物。其通式如下：In order to achieve the purpose of the present invention, the present invention uses phosphalane compounds as starting materials, and generates 1-phospha norbornadiene compounds through phospha D-A reaction. Its general formula is as follows:
Ar为苯基，萘基，被C1-5烷基或C1-5烷氧基取代的苯基。Ar is phenyl, naphthyl, phenyl substituted with C1-5 alkyl or C1-5 alkoxy.
优选：Ar为苯基，萘基，被甲基、丁基或甲氧基或丁氧基取代的苯基。Preferably: Ar is phenyl, naphthyl, phenyl substituted with methyl, butyl or methoxy or butoxy.
方案路线如下:The program route is as follows:
(1)在N2环境下，将甲苯，磷杂环戊二烯A1，化合物A2加入到Schlenk瓶中，130℃-140℃油浴中反应。过柱，得到化合物A3。(1) Under N 2 environment, add toluene, phosphalane A1, and compound A2 into a Schlenk bottle, and react in an oil bath at 130°C-140°C. After passing through the column, compound A3 was obtained.
(2)在N2环境下，将二氯甲烷，化合物A3，盐酸、二氧化硅加入Schlenk瓶中，室温搅拌反应。反应完全后用H2O洗涤，干燥，旋干得化合物A4。(2) Under N 2 environment, dichloromethane, compound A3, hydrochloric acid and silica were added to a Schlenk bottle, and the reaction was stirred at room temperature. After the reaction is complete, wash with H 2 O, dry and spin dry to obtain compound A4.
(3)在N2环境下，将四氢呋喃，化合物A4，R-叔丁基磺酸亚胺，四异丙氧基钛加入Schlenk瓶中，40℃-50℃油浴反应。经萃取，干燥，柱层析法分离得化合物A5。(3) Under N2 environment, add tetrahydrofuran, compound A4, R-tert-butylsulfonic acid imide, and titanium tetraisopropoxide into a Schlenk bottle, and react in an oil bath at 40°C-50°C. After extraction, drying, and column chromatography, compound A5 was obtained.
(4)化合物II-a至II’-g的合成方法，步骤如下：(4) the synthetic method of compound II-a to II'-g, the steps are as follows:
分别取化合物A5于Schlenk瓶中，抽真空，充入氮气，加入四氢呋喃，在-70℃～-78℃的条件下加入芳基锂试剂，在此温度下继续反应，当反应完全，向反应体系加入NH4Cl溶液，然后经萃取，合并有机层，经干燥，过滤，减压蒸去溶剂，柱层析分离，得到相应的产物II和II’。Take compound A5 in a Schlenk bottle, vacuumize, fill with nitrogen, add tetrahydrofuran, add aryllithium reagent under the condition of -70℃～-78℃, continue the reaction at this temperature, when the reaction is complete, add to the reaction system NH 4 Cl solution was added, followed by extraction, the organic layers were combined, dried, filtered, the solvent was evaporated under reduced pressure, and separated by column chromatography to obtain the corresponding products II and II'.
具体得到如下化合物：Specifically, the following compounds were obtained:
本发明优点在于：1、合成方法简单、可行，收率较高，达61％以上；2、目标物II作为一类结构新颖的磷手性中心配体，通过刚性骨架的引入，成功地解决了磷手性中心易于消旋化的科学难题，此类磷手性中心配体是一类有效的手性配体，未来将能够广泛的应用到不对称反应中，具有广阔的商业应用前景。The advantages of the present invention are: 1. The synthesis method is simple and feasible, and the yield is high, reaching more than 61%; 2. The target II, as a novel structural phosphochiral center ligand, is successfully solved by the introduction of a rigid skeleton. In order to solve the scientific problem of easy racemization of phosphorus chiral centers, this kind of phosphorus chiral center ligands is a class of effective chiral ligands, which will be widely used in asymmetric reactions in the future, and have broad commercial application prospects.
具体实施方式Detailed ways
为对本发明进行更好地说明，举实施例如下：In order to better illustrate the present invention, examples are as follows:
实施例1Example 1
(1)在N2环境下，将40mL甲醇，苯丙炔醛(20mmol),原甲酸三甲酯(40mmol)加入100mLSchlenk瓶中，然后加入催化剂对甲苯磺酸(10mol％)，转入65℃油浴回流10h。反应完全后加入少量NaOH固体，继续搅拌20min。减压旋蒸后，过中性氧化铝干柱，旋干后得化合物A2，产率93％。(1) under N2 environment, add 40mL methanol, phenylpropargyl aldehyde (20mmol), trimethyl orthoformate (40mmol) into 100mL Schlenk bottle, then add catalyst p-toluenesulfonic acid (10mol%), transfer to 65 ℃ The oil bath was refluxed for 10h. After the reaction was completed, a small amount of NaOH solid was added, and stirring was continued for 20 min. After rotary evaporation under reduced pressure, it was passed through a neutral alumina dry column, and the compound A2 was obtained after rotary drying with a yield of 93%.
(2)在N2环境下，将5mL甲苯，化合物A2(5.6mmol)，磷杂环戊二烯(5.3mmol)加入75mLSchlenk瓶中。140℃油浴中反应2h。过中性氧化铝柱(PE:DCM＝10:1)，得到化合物A3。产率80％。(2) Under N 2 atmosphere, 5 mL of toluene, compound A2 (5.6 mmol), and phosphole (5.3 mmol) were added to a 75 mL Schlenk bottle. The reaction was carried out in an oil bath at 140°C for 2h. Pass through neutral alumina column (PE:DCM=10:1) to obtain compound A3. Yield 80%.
(3)在N2环境下，将20mL二氯甲烷，化合物A3，盐酸、二氧化硅加入100mL Schlenk瓶中，室温搅拌3h。反应完全后用H2O洗涤(20mL*3)，MgSO4干燥。旋干得化合物A4，产率86％。(3) Under N 2 environment, add 20 mL of dichloromethane, compound A3, hydrochloric acid and silica into a 100 mL Schlenk bottle, and stir at room temperature for 3 h. After the reaction was completed, it was washed with H 2 O (20 mL*3) and dried over MgSO 4 . Spin-dried to obtain compound A4 with a yield of 86%.
1H NMR(CDCl3):d(ppm)-1.4(s,3H),2.1(s,3H),2.2(m,2H),6.8–7.3(m,10H),9.7(d,J-9.2Hz,1H)ppm；13C NMR(CDCl3):d(ppm)-16.5,20.4,65.1,73.6(d,J-5.9Hz),191.0(d,J-16.7Hz)ppm；31P NMR(CDCl3)d(ppm)--31.2ppm. 1 H NMR (CDCl 3 ): d(ppm)-1.4(s, 3H), 2.1(s, 3H), 2.2(m, 2H), 6.8-7.3(m, 10H), 9.7(d, J-9.2 Hz, 1H) ppm; 13 C NMR (CDCl 3 ): d (ppm)-16.5, 20.4, 65.1, 73.6 (d, J-5.9 Hz), 191.0 (d, J-16.7 Hz) ppm; 31 P NMR ( CDCl 3 )d(ppm)--31.2ppm.
(4)在N2环境下，将40mL THF，化合物A4(7.4mmol)，R-叔丁基磺酸亚胺(8mmol)，四异丙氧基钛(16mmol)加入100mLSchlenk瓶中，50℃油浴反应3h。用乙酸乙酯萃取(100mL*3)，MgSO4干燥。柱层析法分离(DCM：EA＝1:1)。得化合物A5，产率61％。(4) Under N 2 environment, add 40 mL of THF, compound A4 (7.4 mmol), R-tert-butylsulfonic imide (8 mmol), and tetraisopropoxide titanium (16 mmol) into a 100 mL Schlenk bottle, oil at 50°C Bath reaction for 3h. Extracted with ethyl acetate (100 mL*3), dried over MgSO4 . Separation by column chromatography (DCM:EA=1:1). Compound A5 was obtained in 61% yield.
(4)化合物II-a至II’-g的合成方法，步骤如下：(4) the synthetic method of compound II-a to II'-g, the steps are as follows:
分别取化合物原料A5于Schlenk瓶中，抽真空，充入氮气，加入四氢呋喃，在-78℃的条件下加入2.0当量的不同芳基锂试剂，在此温度下继续反应10h，当反应完全，向反应体系加入NH4Cl溶液，然后使用乙酸乙酯萃取，合并有机层，使用MgSO4干燥，过滤，减压蒸去溶剂，柱层析分离。得到相应的产物II-a～II’-g。Take compound raw materials A5 into Schlenk bottles respectively, vacuumize, fill with nitrogen, add tetrahydrofuran, add 2.0 equivalents of different aryllithium reagents at -78 °C, continue to react at this temperature for 10 h, when the reaction is complete, add to NH 4 Cl solution was added to the reaction system, followed by extraction with ethyl acetate. The organic layers were combined, dried over MgSO 4 , filtered, evaporated under reduced pressure to remove the solvent, and separated by column chromatography. The corresponding products II-a to II'-g were obtained.
(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(phenyl)methyl)-2-methylpropane-2-sulfinamide(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl) (phenyl)methyl)-2-methylpropane-2-sulfinamide
35％yield；yellow solid35% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-19.75(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-19.75(s)ppm.
1H NMR(300MHz,CDCl3)δ0.86(s,9H),1.30(s,3H),1.88–2.02(m,2H),2.16(s,3H),2.99(s,1H),5.18(d,J＝8.8Hz,1H),7.03(d,J＝6.5Hz,2H),7.21–7.26(m,1H),7.30–7.46(m,10H),7.56(d,J＝7.4Hz,2H)ppm. 1 H NMR (300MHz, CDCl 3 )δ0.86(s,9H), 1.30(s,3H), 1.88-2.02(m,2H), 2.16(s,3H), 2.99(s,1H), 5.18( d, J=8.8Hz, 1H), 7.03 (d, J=6.5Hz, 2H), 7.21–7.26 (m, 1H), 7.30–7.46 (m, 10H), 7.56 (d, J=7.4Hz, 2H) )ppm.
13C NMR(75MHz,CDCl3)δ15.74(s,CH3),20.60(s,CH3),22.26(s,3CH3),55.51(s,C),58.32(d,J＝15.3Hz,CH2),63.93(s,CH),71.04(d,J＝5.2Hz,C),126.52(d,J＝0.8Hz,CH),127.58(d,J＝3.7Hz,2CH),127.74(s,CH),128.24(d,J＝3.5Hz,2CH),128.37(s,2CH),128.37(s,CH),128.39(d,J＝2.6Hz,2CH),128.55(s,2CH),128.64(d,J＝5.7Hz,2CH),137.14(d,J＝1.6Hz,C),138.66(d,J＝20.8Hz,C),140.51(s,C),148.49(d,J＝23.2Hz,C),155.35(d,J＝29.7Hz,C),157.89(s,C),162.79(s,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.74 (s, CH 3 ), 20.60 (s, CH 3 ), 22.26 (s, 3CH 3 ), 55.51 (s, C), 58.32 (d, J=15.3 Hz , CH 2 ), 63.93(s, CH), 71.04(d, J=5.2Hz, C), 126.52(d, J=0.8Hz, CH), 127.58(d, J=3.7Hz, 2CH), 127.74( s,CH),128.24(d,J＝3.5Hz,2CH),128.37(s,2CH),128.37(s,CH),128.39(d,J＝2.6Hz,2CH),128.55(s,2CH), 128.64(d,J＝5.7Hz,2CH),137.14(d,J＝1.6Hz,C),138.66(d,J＝20.8Hz,C),140.51(s,C),148.49(d,J＝23.2 Hz, C), 155.35 (d, J=29.7 Hz, C), 157.89 (s, C), 162.79 (s, C) ppm.
(R)-N-((S)-((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(phenyl)methyl)-2-methylpropane-2-sulfinamide(R)-N-((S)-((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl) (phenyl)methyl)-2-methylpropane-2-sulfinamide
38％yield；yellow solid38% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-20.98(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-20.98(s)ppm.
1H NMR(300MHz,CDCl3)δ0.79(s,9H,3CH3),1.25(s,3H,CH3),1.82(t,J＝9.7Hz,1H),2.00(t,J＝9.9Hz,1H),2.08(s,3H,CH3),3.56(s,1H,NH),5.12(d,J＝9.6Hz,1H,CH),7.09(d,J＝4.2Hz,2H),7.23(t,J＝7.3Hz,1H),7.28–7.48(m,12H)ppm. 1 H NMR (300 MHz, CDCl 3 ) δ 0.79 (s, 9H, 3CH 3 ), 1.25 (s, 3H, CH 3 ), 1.82 (t, J=9.7 Hz, 1H), 2.00 (t, J=9.9 Hz, 1H), 2.08 (s, 3H, CH 3 ), 3.56 (s, 1H, NH), 5.12 (d, J=9.6 Hz, 1H, CH), 7.09 (d, J=4.2 Hz, 2H), 7.23(t,J＝7.3Hz,1H),7.28-7.48(m,12H)ppm.
13C NMR(75MHz,CDCl3)δ15.20(s,CH3),20.59(s,CH3),22.24(s,3CH3),55.64(s,C),57.57(d,J＝13.3Hz,CH),65.54(s,CH2),70.48(d,J＝5.2Hz,C),126.13(d,J＝1.2Hz,CH),127.21(d,J＝4.7Hz,2CH),127.35(s,CH),127.71(d,J＝4.2Hz,2CH),128.14(s,2CH),128.14(s,CH),128.73(s,2CH),128.90(d,J＝3.1Hz,2CH),129.04(d,J＝3.9Hz,2CH),137.65(d,J＝1.6Hz,C),139.58(d,J＝20.4Hz,C),142.60(s,C),148.29(d,J＝22.6Hz,C),154.63(d,J＝31.3Hz,C),158.29(s,C),164.74(d,J＝1.1Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.20 (s, CH 3 ), 20.59 (s, CH 3 ), 22.24 (s, 3CH 3 ), 55.64 (s, C), 57.57 (d, J=13.3 Hz ,CH),65.54(s,CH 2 ),70.48(d,J=5.2Hz,C),126.13(d,J=1.2Hz,CH),127.21(d,J=4.7Hz,2CH),127.35( s,CH),127.71(d,J＝4.2Hz,2CH),128.14(s,2CH),128.14(s,CH),128.73(s,2CH),128.90(d,J＝3.1Hz,2CH), 129.04(d,J＝3.9Hz,2CH),137.65(d,J＝1.6Hz,C),139.58(d,J＝20.4Hz,C),142.60(s,C),148.29(d,J＝22.6 Hz, C), 154.63 (d, J=31.3 Hz, C), 158.29 (s, C), 164.74 (d, J=1.1 Hz, C) ppm.
(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(p-tolyl)methyl)-2-methylpropane-2-sulfinamide(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl) (p-tolyl)methyl)-2-methylpropane-2-sulfinamide
34％yield；yellow solid34% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-19.51(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-19.51(s)ppm.
1H NMR(300MHz,CDCl3)δ0.85(s,9H),1.28(s,3H),1.94(p,J＝9.8Hz,2H),2.15(s,3H),2.37(s,3H),2.97(s,1H),5.15(d,J＝8.8Hz,1H),7.01(d,J＝6.6Hz,2H),7.17(d,J＝7.8Hz,2H),7.21–7.46(m,11H)ppm. 1 H NMR (300MHz, CDCl 3 ) δ 0.85(s, 9H), 1.28(s, 3H), 1.94(p, J=9.8Hz, 2H), 2.15(s, 3H), 2.37(s, 3H) ,2.97(s,1H),5.15(d,J＝8.8Hz,1H),7.01(d,J＝6.6Hz,2H),7.17(d,J＝7.8Hz,2H),7.21–7.46(m, 11H)ppm.
13C NMR(75MHz,CDCl3)δ15.72(s,CH3),20.60(s,CH3),21.27(s,CH3),22.26(s,3CH3),55.45(s,C),58.07(d,J＝15.5Hz,CH),63.84(s,CH2),70.99(d,J＝5.2Hz,C),126.47(d,J＝0.9Hz,CH),127.49(d,J＝6.2Hz,2CH),128.21(d,J＝4.9Hz,2CH),128.32(s,2CH),128.32(s,CH),128.35(s,2CH),128.49(d,J＝5.5Hz,2CH),129.29(s,2CH),137.20(d,J＝1.5Hz,C),137.41(s,C),137.41(s,C),138.68(d,J＝20.8Hz,C),148.54(d,J＝20.1Hz,C),155.49(d,J＝29.4Hz,C),157.82(s,C),162.31(d,J＝0.8Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.72 (s, CH 3 ), 20.60 (s, CH 3 ), 21.27 (s, CH 3 ), 22.26 (s, 3CH 3 ), 55.45 (s, C), 58.07(d,J=15.5Hz,CH),63.84(s,CH 2 ),70.99(d,J=5.2Hz,C),126.47(d,J=0.9Hz,CH),127.49(d,J= 6.2Hz, 2CH), 128.21(d, J＝4.9Hz, 2CH), 128.32(s, 2CH), 128.32(s, CH), 128.35(s, 2CH), 128.49(d, J＝5.5Hz, 2CH) ,129.29(s,2CH),137.20(d,J＝1.5Hz,C),137.41(s,C),137.41(s,C),138.68(d,J＝20.8Hz,C),148.54(d, J=20.1Hz, C), 155.49 (d, J=29.4Hz, C), 157.82 (s, C), 162.31 (d, J=0.8Hz, C) ppm.
(R)-2-methyl-N-((S)-(5-methyl-3,6-diphenyl-4H-1l2-phosphinin-2-yl)(p-tolyl)methyl)propane-2-sulfinamide(R)-2-methyl-N-((S)-(5-methyl-3,6-diphenyl-4H-1l2-phosphinin-2-yl)(p-tolyl)methyl)propane-2-sulfinamide
27％yield；yellow solid27% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-20.87(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-20.87(s)ppm.
1H NMR(300MHz,CDCl3)δ0.76(s,9H,3CH3),1.23(s,3H,CH3),1.81(t,J＝9.7Hz,1H),1.98(t,J＝9.9Hz,1H),2.06(s,3H,CH3),2.34(s,3H,CH3),3.51(s,1H,NH),5.07(d,J＝9.7Hz,1H,CH),7.05–7.14(m,4H),7.18–7.23(m,1H),7.29–7.46(m,9H)ppm. 1 H NMR (300 MHz, CDCl 3 ) δ 0.76 (s, 9H, 3CH 3 ), 1.23 (s, 3H, CH 3 ), 1.81 (t, J=9.7 Hz, 1H), 1.98 (t, J=9.9 Hz, 1H), 2.06 (s, 3H, CH 3 ), 2.34 (s, 3H, CH 3 ), 3.51 (s, 1H, NH), 5.07 (d, J=9.7 Hz, 1H, CH), 7.05– 7.14(m,4H),7.18–7.23(m,1H),7.29–7.46(m,9H)ppm.
13C NMR(75MHz,CDCl3)δ15.17(s,CH3),20.58(s,CH3),21.16(s,CH3),22.23(s,3CH3),55.59(s,C),57.28(d,J＝13.3Hz,CH),65.53(s,CH2),70.43(d,J＝5.1Hz,C),126.10(d,J＝1.1Hz,CH),127.06(d,J＝6.6Hz,2CH),127.19(d,J＝4.3Hz,2CH),127.30(s,CH),128.12(s,2CH),128.89(d,J＝3.7Hz,2CH),129.04(d,J＝3.9Hz,2CH),129.39(s,2CH),137.45(s,C),137.68(d,J＝1.6Hz,C),139.60(d,J＝20.3Hz,C),139.71(s,C),148.31(d,J＝22.7Hz,C),154.74(d,J＝31.0Hz,C),158.27(s,C),164.45(d,J＝1.2Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.17 (s, CH 3 ), 20.58 (s, CH 3 ), 21.16 (s, CH 3 ), 22.23 (s, 3CH 3 ), 55.59 (s, C), 57.28 (d, J=13.3 Hz, CH), 65.53 (s, CH 2 ), 70.43 (d, J= 5.1 Hz, C), 126.10 (d, J= 1.1 Hz, CH), 127.06 (d, J= 6.6Hz, 2CH), 127.19(d, J＝4.3Hz, 2CH), 127.30(s, CH), 128.12(s, 2CH), 128.89(d, J＝3.7Hz, 2CH), 129.04(d, J＝ 3.9Hz, 2CH), 129.39(s, 2CH), 137.45(s, C), 137.68(d, J=1.6Hz, C), 139.60(d, J=20.3Hz, C), 139.71(s, C) ,148.31(d,J＝22.7Hz,C),154.74(d,J＝31.0Hz,C),158.27(s,C),164.45(d,J＝1.2Hz,C)ppm.
(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(4-methoxyphenyl)methyl)-2-methylpropane-2-sulfinamide(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl) (4-methoxyphenyl)methyl)-2-methylpropane-2-sulfinamide
39％yield；yellow solid39% yield; yellow solid
31PNMR(121MHz,CDCl3)δ-21.03(s)ppm. 31 PNMR (121MHz, CDCl 3 )δ-21.03(s)ppm.
1H NMR(300MHz,CDCl3)δ0.78(s,9H,3CH3),1.25(s,3H,CH3),1.83(t,J＝9.7Hz,1H),2.00(t,J＝9.9Hz,1H),2.07(d,J＝8.9Hz,3H,CH3),3.51(s,1H,NH),3.81(s,3H,OCH3),5.08(d,J＝9.7Hz,1H,CH),6.87(d,J＝8.6Hz,2H),7.08(d,J＝4.9Hz,2H),7.20–7.47(m,11H)ppm. 1 H NMR (300MHz, CDCl3) δ 0.78 (s, 9H, 3CH 3 ), 1.25 (s, 3H, CH 3 ), 1.83 (t, J=9.7Hz, 1H), 2.00 (t, J=9.9Hz , 1H), 2.07 (d, J=8.9Hz, 3H, CH 3 ), 3.51 (s, 1H, NH), 3.81 (s, 3H, OCH 3 ), 5.08 (d, J=9.7 Hz, 1H, CH ),6.87(d,J＝8.6Hz,2H),7.08(d,J＝4.9Hz,2H),7.20–7.47(m,11H)ppm.
13C NMR(75MHz,CDCl3)δ15.20(s,CH3),20.60(s,CH3),22.23(s,3CH3),55.24(s,OCH3),55.57(s,C),56.97(d,J＝13.4Hz,CH),65.54(s,CH2),70.42(d,J＝5.1Hz,C),114.04(s,2CH),126.12(d,J＝1.0Hz,CH),127.31(s,CH),128.14(s,2CH),128.29(d,J＝3.5Hz,2CH),128.41(d,J＝4.2Hz,2CH),128.89(d,J＝5.1Hz,2CH),129.05(d,J＝4.5Hz,2CH),134.85(s,C),137.69(d,J＝1.6Hz,C),139.60(d,J＝20.4Hz,C),148.28(d,J＝22.8Hz,C),154.87(d,J＝31.1Hz,C),158.27(s,C),159.09(s,C),164.21(d,J＝1.1Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.20 (s, CH 3 ), 20.60 (s, CH 3 ), 22.23 (s, 3CH 3 ), 55.24 (s, OCH 3 ), 55.57 (s, C), 56.97(d,J=13.4Hz,CH),65.54(s,CH 2 ),70.42(d,J=5.1Hz,C),114.04(s,2CH),126.12(d,J=1.0Hz,CH) ,127.31(s,CH),128.14(s,2CH),128.29(d,J＝3.5Hz,2CH),128.41(d,J＝4.2Hz,2CH),128.89(d,J＝5.1Hz,2CH) ,129.05(d,J＝4.5Hz,2CH),134.85(s,C),137.69(d,J＝1.6Hz,C),139.60(d,J＝20.4Hz,C),148.28(d,J＝ 22.8Hz,C), 154.87(d,J=31.1Hz,C), 158.27(s,C), 159.09(s,C), 164.21(d,J=1.1Hz,C)ppm.
(R)-N-((S)-(4-methoxyphenyl)(5-methyl-3,6-diphenyl-4H-1l2-phosphinin-2-yl)methyl)-2-methylpropane-2-sulfinamide(R)-N-((S)-(4-methoxyphenyl)(5-methyl-3,6-diphenyl-4H-1l2-phosphinin-2-yl)methyl)-2-methylpropane-2-sulfinamide
25％yield；yellow solid25% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-21.05(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-21.05(s)ppm.
1H NMR(300MHz,CDCl3)δ0.77(s,9H,3CH3),1.24(s,3H,CH3),1.83(t,J＝9.7Hz,1H),2.00(t,J＝9.9Hz,1H),2.08(s,3H,CH3),3.50(s,1H,NH),3.81(s,3H,OCH3),5.07(d,J＝9.7Hz,1H,CH),6.87(d,J＝8.7Hz,2H),7.07(d,J＝5.9Hz,2H),7.22(t,J＝7.2Hz,1H),7.32–7.46(m,9H)ppm. 1 H NMR (300 MHz, CDCl 3 ) δ 0.77 (s, 9H, 3CH 3 ), 1.24 (s, 3H, CH 3 ), 1.83 (t, J=9.7 Hz, 1H), 2.00 (t, J=9.9 Hz, 1H), 2.08 (s, 3H, CH 3 ), 3.50 (s, 1H, NH), 3.81 (s, 3H, OCH 3 ), 5.07 (d, J=9.7 Hz, 1H, CH ), 6.87 ( d,J＝8.7Hz,2H),7.07(d,J＝5.9Hz,2H),7.22(t,J＝7.2Hz,1H),7.32–7.46(m,9H)ppm.
13C NMR(75MHz,CDCl3)δ15.17(s,CH3),20.58(s,CH3),22.22(s,3CH3),55.25(s,OCH3),55.57(s,C),56.95(d,J＝13.5Hz,CH),65.53(s,CH2),70.41(d,J＝5.1Hz,C),114.02(s,2CH),126.10(d,J＝1.2Hz,CH),127.30(s,CH),128.13(s,2CH),128.29(d,J＝4.7Hz,2CH),128.42(d,J＝4.8Hz,2CH),128.87(d,J＝5.7Hz,2CH),128.99(d,J＝2.8Hz,CH),134.85(s,C),137.68(d,J＝1.7Hz,C),139.58(d,J＝20.4Hz,C),148.25(d,J＝22.8Hz,C),154.85(d,J＝31.1Hz,C),158.29(s,C),159.07(s,C),164.22(d,J＝1.2Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.17 (s, CH 3 ), 20.58 (s, CH 3 ), 22.22 (s, 3CH 3 ), 55.25 (s, OCH 3 ), 55.57 (s, C), 56.95(d,J=13.5Hz,CH),65.53(s,CH 2 ),70.41(d,J=5.1Hz,C),114.02(s,2CH),126.10(d,J=1.2Hz,CH) ,127.30(s,CH),128.13(s,2CH),128.29(d,J＝4.7Hz,2CH),128.42(d,J＝4.8Hz,2CH),128.87(d,J＝5.7Hz,2CH) ,128.99(d,J＝2.8Hz,CH),134.85(s,C),137.68(d,J＝1.7Hz,C),139.58(d,J＝20.4Hz,C),148.25(d,J＝ 22.8Hz,C), 154.85(d,J=31.1Hz,C), 158.29(s,C), 159.07(s,C), 164.22(d,J=1.2Hz,C)ppm.
(S)-N-((R)-(4-butylphenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide(S)-N-((R)-(4-butylphenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien -2-yl)methyl)-2-methylpropane-2-sulfinamide
30％yield；yellow solid30% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-19.78(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-19.78(s)ppm.
1H NMR(300MHz,CDCl3)δ0.86(s,9H,3CH3),0.97(t,J＝7.3Hz,3H,CH3),1.30(s,3H,CH3),1.41(dd,J＝14.8,7.4Hz,2H,CH2),1.65(dt,J＝15.3,7.5Hz,2H,CH2),1.90–2.02(m,2H,CH2),2.17(s,3H,3CH3),2.61–2.66(m,2H),2.98(s,1H,NH),5.16(d,J＝8.9Hz,1H,CH),7.04(d,J＝6.5Hz,2H),7.17–7.27(m,3H),7.35–7.48(m,9H)ppm. 1 H NMR (300 MHz, CDCl 3 ) δ 0.86 (s, 9H, 3CH 3 ), 0.97 (t, J=7.3 Hz, 3H, CH 3 ), 1.30 (s, 3H, CH 3 ), 1.41 (dd, J=14.8, 7.4Hz, 2H, CH2 ), 1.65 (dt, J=15.3, 7.5Hz, 2H, CH2 ), 1.90-2.02 (m, 2H, CH2 ), 2.17 (s, 3H , 3CH3 ), 2.61–2.66 (m, 2H), 2.98 (s, 1H, NH), 5.16 (d, J=8.9Hz, 1H, CH), 7.04 (d, J=6.5Hz, 2H), 7.17–7.27 ( m,3H),7.35–7.48(m,9H)ppm.
13C NMR(75MHz,CDCl3)δ14.05(s,CH3),15.72(s,CH3),20.62(s,CH3),22.29(s,3CH3),22.57(s,CH2),33.49(s,CH2),35.44(s,CH2),55.45(s,C),58.09(d,J＝15.4Hz,CH),63.92(s,CH2),70.96(d,J＝5.2Hz,C),126.45(d,J＝4.4Hz,CH),127.54(s,CH),128.32(d,J＝3.0Hz,2CH),128.34(s,2CH),128.36(s,2CH),128.38(d,J＝3.3Hz,2CH),128.42(d,J＝2.1Hz,2CH),128.53(s,2CH),137.19(d,J＝1.7Hz,C),137.57(s,C),138.71(d,J＝20.8Hz,C),142.36(s,C),148.54(d,J＝23.3Hz,C),155.52(d,J＝29.5Hz,C),157.82(s,C),162.36(d,J＝0.8Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 14.05 (s, CH 3 ), 15.72 (s, CH 3 ), 20.62 (s, CH 3 ), 22.29 (s, 3CH 3 ), 22.57 (s, CH 2 ) ,33.49(s,CH 2 ),35.44(s,CH 2 ),55.45(s,C),58.09(d,J=15.4Hz,CH),63.92(s,CH 2 ),70.96(d,J= 5.2Hz,C),126.45(d,J=4.4Hz,CH),127.54(s,CH),128.32(d,J=3.0Hz,2CH),128.34(s,2CH),128.36(s,2CH) ,128.38(d,J＝3.3Hz,2CH),128.42(d,J＝2.1Hz,2CH),128.53(s,2CH),137.19(d,J＝1.7Hz,C),137.57(s,C) ,138.71(d,J＝20.8Hz,C),142.36(s,C),148.54(d,J＝23.3Hz,C),155.52(d,J＝29.5Hz,C),157.82(s,C) ,162.36(d,J＝0.8Hz,C)ppm.
(R)-N-((S)-(4-butylphenyl)((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide(R)-N-((S)-(4-butylphenyl)((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien -2-yl)methyl)-2-methylpropane-2-sulfinamide
35％yield；yellow solid35% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-20.86(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-20.86(s)ppm.
1H NMR(300MHz,CDCl3)δ0.79(s,9H,3CH3),0.95(t,J＝7.3 Hz,3H,CH3),1.25(s,3H,CH3),1.40(dt,J＝14.7,7.2Hz,2H,CH2),1.62(dt,J＝15.3,7.5Hz,2H,CH2),1.92(dt,J＝47.3,9.7Hz,2H,CH2),2.09(s,3H,CH3),2.59–2.64(m,2H,CH2),3.54(s,1H,NH),5.10(d,J＝9.7Hz,1H,CH),7.02–7.17(m,4H),7.23(t,J＝7.2Hz,1H),7.31–7.48(m,9H)ppm. 1 H NMR (300 MHz, CDCl 3 ) δ 0.79 (s, 9H, 3CH 3 ), 0.95 (t, J=7.3 Hz, 3H, CH 3 ), 1.25 (s, 3H, CH 3 ), 1.40 (dt, J=14.7, 7.2Hz, 2H, CH2 ), 1.62 (dt, J=15.3, 7.5Hz, 2H, CH2 ), 1.92 (dt, J=47.3, 9.7Hz, 2H, CH2 ), 2.09 (s , 3H, CH 3 ), 2.59–2.64 (m, 2H, CH 2 ), 3.54 (s, 1H, NH), 5.10 (d, J=9.7Hz, 1H, CH), 7.02–7.17 (m, 4H) ,7.23(t,J＝7.2Hz,1H),7.31–7.48(m,9H)ppm.
13C NMR(75MHz,CDCl3)δ14.00(s,CH3),15.19(s,CH3),20.61(s,CH3),22.25(s,3CH3),22.49(s,CH2),33.56(s,CH2),35.38(s,CH2),55.59(s,C),57.30(d,J＝13.4Hz,CH),65.54(s,CH2),70.42(d,J＝5.2Hz,C),126.10(d,J＝0.9Hz),127.02(d,J＝5.5Hz),127.15(d,J＝4.2Hz),127.31(s),128.13(s),128.71(s),128.90(d,J＝4.1Hz),129.07(d,J＝6.0Hz),137.70(d,J＝1.6Hz),139.62(d,J＝20.3Hz),139.84(s),142.44(s),148.31(d,J＝20.3Hz),154.75(d,J＝31.1Hz),158.25(s),164.39(d,J＝1.0Hz)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 14.00 (s, CH 3 ), 15.19 (s, CH 3 ), 20.61 (s, CH 3 ), 22.25 (s, 3CH 3 ), 22.49 (s, CH 2 ) ,33.56(s,CH 2 ),35.38(s,CH 2 ),55.59(s,C),57.30(d,J=13.4Hz,CH),65.54(s,CH 2 ),70.42(d,J= 5.2Hz, C), 126.10(d, J=0.9Hz), 127.02(d, J=5.5Hz), 127.15(d, J=4.2Hz), 127.31(s), 128.13(s), 128.71(s) ,128.90(d,J＝4.1Hz),129.07(d,J＝6.0Hz),137.70(d,J＝1.6Hz),139.62(d,J＝20.3Hz),139.84(s),142.44(s) ,148.31(d,J=20.3Hz),154.75(d,J=31.1Hz),158.25(s),164.39(d,J=1.0Hz)ppm.
(S)-N-((R)-(4-(tert-butyl)phenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide(S)-N-((R)-(4-(tert-butyl)phenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta- 2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
39％yield；yellow solid39% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-19.77(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-19.77(s)ppm.
1H NMR(300MHz,CDCl3)δ0.83(s,9H,3CH3),1.27(s,3H,CH3),1.32(s,9H,3CH3),1.89–2.00(m,2H,CH2),2.13(s,3H,CH3),2.95(s,1H,NH),5.13(d,J＝9.0Hz,1H,CH),7.02(d,J＝4.9Hz,2H),7.21(dd,J＝14.7,7.8Hz,1H),7.29–7.44(m,11H)ppm. 1 H NMR (300 MHz, CDCl 3 ) δ 0.83 (s, 9H, 3CH 3 ), 1.27 (s, 3H, CH 3 ), 1.32 (s, 9H, 3CH 3 ), 1.89-2.00 (m, 2H, CH 3 ) 2 ), 2.13(s, 3H, CH 3 ), 2.95(s, 1H, NH), 5.13(d, J=9.0Hz, 1H, CH), 7.02(d, J=4.9Hz, 2H), 7.21( dd,J=14.7,7.8Hz,1H),7.29-7.44(m,11H)ppm.
13C NMR(75MHz,CDCl3)δ15.68(s,CH3),20.62(s,CH3),22.30(s,3CH3),31.41(s,3CH3),34.54(s,C),55.46(s,C),57.99(d,J＝15.6Hz,CH),64.06(s,CH2),70.95(d,J＝5.2Hz,C),125.37(s,2CH),126.41(d,J＝4.0Hz,CH),127.49(s,CH),128.03(d,J＝5.2Hz,2CH),128.30(s,2CH),128.30(s,2CH),128.32(s,2CH),128.45(d,J＝3.0Hz,2CH),137.20(d,J＝4.2Hz,C),137.29(s,C),138.71(d,J＝24.9Hz,C),148.39(d,J＝18.0Hz,C),150.39(s,C),155.48(d,J＝29.4Hz,C),157.82(s,C),162.29(s,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.68 (s, CH 3 ), 20.62 (s, CH 3 ), 22.30 (s, 3CH 3 ), 31.41 (s, 3CH 3 ), 34.54 (s, C), 55.46(s, C), 57.99(d, J=15.6Hz, CH), 64.06(s, CH 2 ), 70.95(d, J=5.2Hz, C), 125.37(s, 2CH), 126.41(d, J＝4.0Hz, CH), 127.49(s, CH), 128.03(d, J＝5.2Hz, 2CH), 128.30(s, 2CH), 128.30(s, 2CH), 128.32(s, 2CH), 128.45( d,J＝3.0Hz,2CH),137.20(d,J＝4.2Hz,C),137.29(s,C),138.71(d,J＝24.9Hz,C),148.39(d,J＝18.0Hz, C),150.39(s,C),155.48(d,J=29.4Hz,C),157.82(s,C),162.29(s,C)ppm.
(R)-N-((S)-(4-(tert-butyl)phenyl)((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide(R)-N-((S)-(4-(tert-butyl)phenyl)((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta- 2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
47％yield；yellow solid47% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-20.37(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-20.37(s)ppm.
1H NMR(300MHz,CDCl3)δ0.78(s,9H,3CH3),1.26(s,3H,CH3),1.34(s,9H,3CH3),1.93(dt,J＝42.1,9.8Hz,2H,CH2),2.09(s,3H,CH3),3.55(s,1H,NH),5.11(d,J＝9.7Hz,1H,CH),7.11(d,J＝6.2Hz,2H),7.22(t,J＝7.1Hz,1H),7.31–7.48(m,11H)ppm. 1 H NMR (300 MHz, CDCl 3 ) δ 0.78 (s, 9H, 3CH 3 ), 1.26 (s, 3H, CH 3 ), 1.34 (s, 9H, 3CH 3 ), 1.93 (dt, J=42.1, 9.8 Hz, 2H, CH 2 ), 2.09 (s, 3H, CH 3 ), 3.55 (s, 1H, NH), 5.11 (d, J=9.7 Hz, 1H, CH), 7.11 (d, J=6.2 Hz, 2H), 7.22(t, J=7.1Hz, 1H), 7.31–7.48(m, 11H) ppm.
13C NMR(75MHz,CDCl3)δ15.19(s,CH3),20.62(s,CH3),22.26(s,3CH3),31.36(s,3CH3),34.55(s,C),55.59(s,C),57.21(d,J＝13.5Hz,CH),65.56(s,CH2),70.43(d,J＝5.1Hz,C),125.60(s,2CH),126.09(d,J＝1.0Hz,CH),126.77(d,J＝6.6Hz,2CH),126.92(d,J＝6.5Hz,2CH),127.30(s,CH),128.12(s,2CH),128.89(d,J＝6.1Hz,2CH),129.07(d,J＝6.4Hz,2CH),137.69(d,J＝1.5Hz,C),139.53(s,C),139.63(d,J＝20.3Hz,C),148.34(d,J＝22.7Hz,C),150.43(d,J＝12.0Hz,C),154.66(d,J＝31.0Hz,C),158.21(s,C),164.39(d,J＝0.6Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.19(s, CH 3 ), 20.62(s, CH 3 ), 22.26(s, 3CH 3 ), 31.36(s, 3CH 3 ), 34.55(s, C), 55.59(s, C), 57.21(d, J=13.5Hz, CH), 65.56(s, CH 2 ), 70.43(d, J=5.1 Hz, C), 125.60(s, 2CH), 126.09(d, J＝1.0Hz, CH), 126.77(d, J＝6.6Hz, 2CH), 126.92(d, J＝6.5Hz, 2CH), 127.30(s, CH), 128.12(s, 2CH), 128.89(d, J＝6.1Hz, 2CH), 129.07(d, J＝6.4Hz, 2CH), 137.69(d, J＝1.5Hz, C), 139.53(s, C), 139.63(d, J＝20.3Hz, C) ,148.34(d,J＝22.7Hz,C),150.43(d,J＝12.0Hz,C),154.66(d,J＝31.0Hz,C),158.21(s,C),164.39(d,J＝ 0.6Hz,C)ppm.
(S)-N-((R)-(4-(tert-butoxy)phenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide(S)-N-((R)-(4-(tert-butoxy)phenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta- 2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
37％yield；yellow solid37% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-19.86(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-19.86(s)ppm.
1H NMR(300MHz,CDCl3)δ0.82(s,9H),1.28(s,3H),1.36(s,9H),2.02–1.86(m,2H),2.14(s,3H),2.92(d,J＝2.2Hz,1H),5.10(dd,J＝9.0,2.2Hz,1H),7.04–6.90(m,4H),7.42–7.18(m,10H)ppm. 1 H NMR (300MHz, CDCl 3 )δ0.82(s,9H), 1.28(s,3H), 1.36(s,9H), 2.02-1.86(m,2H), 2.14(s,3H), 2.92( d, J=2.2Hz, 1H), 5.10 (dd, J=9.0, 2.2Hz, 1H), 7.04–6.90 (m, 4H), 7.42–7.18 (m, 10H) ppm.
13C NMR(75MHz,CDCl3)δ15.69(s,CH3),20.59(s,CH3),22.25(s,3CH3),28.91(s,3CH3),55.39(s,C),57.74(d,J＝15.2Hz,CH),63.96(s,CH2),70.92(d,J＝5.2Hz,C),78.34(d,J＝2.1Hz,C),123.74(s,2CH),126.48(d,J＝1.1Hz,CH),127.52(s,CH),128.30(d,J＝5.6Hz,2CH),128.34(s,2CH),128.34(s,2CH),128.36(d,J＝2.5Hz,2CH),129.04(d,J＝5.7Hz,2CH),135.06(s,C),137.09(d,J＝1.6Hz,C),138.69(d,J＝20.8Hz,C),148.44(d,J＝21.7Hz,C),154.95(s,C),155.44(d,J＝29.7Hz,C),157.86(s,C),162.52(d,J＝0.8Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.69(s, CH 3 ), 20.59(s, CH 3 ), 22.25(s, 3CH 3 ), 28.91(s, 3CH 3 ), 55.39(s, C), 57.74(d,J=15.2Hz,CH),63.96(s,CH 2 ),70.92(d,J=5.2Hz,C),78.34(d,J=2.1Hz,C),123.74(s,2CH) ,126.48(d,J＝1.1Hz,CH),127.52(s,CH),128.30(d,J＝5.6Hz,2CH),128.34(s,2CH),128.34(s,2CH),128.36(d, J＝2.5Hz, 2CH), 129.04(d, J＝5.7Hz, 2CH), 135.06(s, C), 137.09(d, J＝1.6Hz, C), 138.69(d, J＝20.8Hz, C) ,148.44(d,J＝21.7Hz,C),154.95(s,C),155.44(d,J＝29.7Hz,C),157.86(s,C),162.52(d,J＝0.8Hz,C) ppm.
(S)-N-((R)-(4-(tert-butoxy)phenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide(S)-N-((R)-(4-(tert-butoxy)phenyl)((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta- 2,5-dien-2-yl)methyl)-2-methylpropane-2-sulfinamide
39％yield；yellow solid39% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-21.08(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-21.08(s)ppm.
1H NMR(300MHz,CDCl3)δ0.78(s,9H,3CH3),1.25(s,3H,CH3),1.36(s,9H,3CH3),1.81(t,J＝9.7Hz,1H),1.99(t,J＝9.8Hz,1H),2.07(s,3H,CH3),3.52(d,J＝1.4Hz,1H,NH),5.08(dd,J＝9.7,1.3Hz,1H,CH),6.94(d,J＝8.5Hz,2H),7.08(d,J＝4.8Hz,2H),7.22(t,J＝7.3Hz,1H),7.28–7.32(m,2H),7.34–7.47(m,6H)ppm. 1 H NMR (300 MHz, CDCl 3 ) δ 0.78 (s, 9H, 3CH 3 ), 1.25 (s, 3H, CH 3 ), 1.36 (s, 9H, 3CH 3 ), 1.81 (t, J=9.7 Hz, 1H), 1.99 (t, J=9.8Hz, 1H), 2.07 (s, 3H, CH 3 ), 3.52 (d, J=1.4Hz, 1H, NH), 5.08 (dd, J=9.7, 1.3Hz, 1H,CH),6.94(d,J=8.5Hz,2H),7.08(d,J=4.8Hz,2H),7.22(t,J=7.3Hz,1H),7.28–7.32(m,2H), 7.34–7.47(m,6H)ppm.
13C NMR(75MHz,CDCl3)δ15.08(d,J＝16.7Hz,CH3),20.59(s,CH3),22.25(s,3CH3),28.90(s,3CH3),55.57(s,C),57.01(d,J＝13.5Hz,CH),65.55(s,CH2),70.40(d,J＝5.1Hz,C),78.41(d,J＝7.6Hz,C),123.95(s,2CH),126.12(d,J＝4.3Hz,CH),127.29(s,CH),127.58(d,J＝3.7Hz,2CH),127.70(d,J＝4.6Hz,2CH),128.12(s,2CH),128.89(d,J＝4.2Hz,2CH),129.03(d,J＝3.5Hz,2CH),137.21(s,C),137.66(d,J＝1.7Hz,C),139.59(d,J＝20.4Hz,C),148.25(d,J＝22.6Hz,C),154.85(d,J＝31.1Hz,C),154.97(s,C),158.28(s,C),164.24(d,J＝1.1 Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.08 (d, J=16.7 Hz, CH 3 ), 20.59 (s, CH 3 ), 22.25 (s, 3CH 3 ), 28.90 (s, 3CH 3 ), 55.57 ( s, C), 57.01 (d, J=13.5 Hz, CH), 65.55 (s, CH 2 ), 70.40 (d, J=5.1 Hz, C), 78.41 (d, J=7.6 Hz, C), 123.95 (s,2CH),126.12(d,J＝4.3Hz,CH),127.29(s,CH),127.58(d,J＝3.7Hz,2CH),127.70(d,J＝4.6Hz,2CH),128.12 (s,2CH),128.89(d,J＝4.2Hz,2CH),129.03(d,J＝3.5Hz,2CH),137.21(s,C),137.66(d,J＝1.7Hz,C),139.59 (d,J＝20.4Hz,C),148.25(d,J＝22.6Hz,C),154.85(d,J＝31.1Hz,C),154.97(s,C),158.28(s,C),164.24 (d,J=1.1 Hz,C)ppm.
(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(naphthalen-2-yl)methyl)-2-methylpropane-2-sulfinamide(S)-N-((R)-((1S,4R)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl) (naphthalen-2-yl)methyl)-2-methylpropane-2-sulfinamide
33％yield；yellow solid33% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-18.94(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-18.94(s)ppm.
1H NMR(300MHz,CDCl3)δ0.87(s,9H),1.28(s,3H),1.93(dt,J＝24.8,9.9Hz,2H),2.15(s,3H),3.10(d,J＝1.6Hz,1H),5.36(d,J＝10.0Hz,1H),7.04(d,J＝6.6Hz,2H),7.18–7.53(m,10H),7.75–7.91(m,5H)ppm. 1 H NMR (300MHz, CDCl 3 )δ0.87(s, 9H), 1.28(s, 3H), 1.93(dt, J=24.8, 9.9Hz, 2H), 2.15(s, 3H), 3.10(d, J=1.6Hz, 1H), 5.36 (d, J=10.0Hz, 1H), 7.04 (d, J=6.6Hz, 2H), 7.18–7.53 (m, 10H), 7.75–7.91 (m, 5H)ppm .
13C NMR(75MHz,CDCl3)δ15.76(s,CH3),20.56(s,CH3),22.26(s,3CH3),55.51(s,C),58.64(d,J＝15.7Hz,CH),63.90(s,CH2),71.13(d,J＝5.2Hz,C),126.05(d,J＝2.7Hz,2CH),126.19(d,J＝7.6Hz,CH),126.48(d,J＝4.0Hz,CH),127.65(d,J＝3.8Hz,2CH),127.78(d,J＝3.4Hz,CH),128.16(s,2CH),128.28(s,CH),128.32(s,2CH),128.32(s,CH),128.36(s,CH),128.43(s,CH),133.06(s,C),133.37(s,C),137.27(d,J＝1.6Hz,C),137.89(s,C),138.60(d,J＝20.8Hz,C),148.57(d,J＝23.3Hz,C),155.19(d,J＝29.8Hz,C),157.86(s,C),162.97(d,J＝1.0Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.76 (s, CH 3 ), 20.56 (s, CH 3 ), 22.26 (s, 3CH 3 ), 55.51 (s, C), 58.64 (d, J=15.7 Hz , CH), 63.90(s, CH 2 ), 71.13(d, J=5.2Hz, C), 126.05(d, J=2.7Hz, 2CH), 126.19(d, J=7.6Hz, CH), 126.48( d,J＝4.0Hz,CH),127.65(d,J＝3.8Hz,2CH),127.78(d,J＝3.4Hz,CH),128.16(s,2CH),128.28(s,CH),128.32( s,2CH),128.32(s,CH),128.36(s,CH),128.43(s,CH),133.06(s,C),133.37(s,C),137.27(d,J=1.6Hz,C ),137.89(s,C),138.60(d,J＝20.8Hz,C),148.57(d,J＝23.3Hz,C),155.19(d,J＝29.8Hz,C),157.86(s,C ),162.97(d,J＝1.0Hz,C)ppm.
(R)-N-((S)-((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl)(naphthalen-2-yl)methyl)-2-methylpropane-2-sulfinamide(R)-N-((S)-((1R,4S)-4,5-dimethyl-3,6-diphenyl-1-phosphabicyclo[2.2.1]hepta-2,5-dien-2-yl) (naphthalen-2-yl)methyl)-2-methylpropane-2-sulfinamide
30％yield；yellow solid30% yield; yellow solid
31P NMR(121MHz,CDCl3)δ-20.55(s)ppm. 31 P NMR (121MHz, CDCl 3 )δ-20.55(s)ppm.
1H NMR(300MHz,CDCl3)δ0.83(s,9H),1.25(s,3H),1.78(dd,J＝18.1,8.4Hz,1H),2.00(t,J＝9.9Hz,1H),2.09(s,3H),3.66(s,1H),5.30(d,J＝10.1Hz,1H),7.13–7.27(m,3H),7.35-7.51(m,10H),7.63(dd,J＝8.5,1.2Hz,1H),7.80–7.85(m,4H)ppm. 1 H NMR (300 MHz, CDCl 3 ) δ 0.83 (s, 9H), 1.25 (s, 3H), 1.78 (dd, J=18.1, 8.4 Hz, 1H), 2.00 (t, J=9.9 Hz, 1H) ,2.09(s,3H),3.66(s,1H),5.30(d,J＝10.1Hz,1H),7.13-7.27(m,3H),7.35-7.51(m,10H),7.63(dd,J =8.5,1.2Hz,1H),7.80-7.85(m,4H)ppm.
13C NMR(75MHz,CDCl3)δ15.21(s,CH3),20.57(s,CH3),22.27(s,3CH3),55.70(s,C),57.76(d,J＝13.3Hz,CH),65.52(s,CH2),70.54(d,J＝5.2Hz,C),125.44(d,J＝5.9Hz,CH),125.82(d,J＝3.6Hz,CH),126.06(s,CH),126.21(d,J＝5.8Hz,2CH),127.42(s,CH),127.67(s,CH),128.17(s,2CH),128.17(s,2CH),128.51(d,J＝4.3Hz,2CH),128.94(s,CH),129.04(s,CH),133.00(s,C),133.41(s,C),137.71(d,J＝1.6Hz,C),139.62(d,J＝20.4Hz,C),140.06(s,C),148.43(d,J＝22.9Hz,C),154.64(d,J＝31.6Hz,C),158.33(s,C),165.04(d,J＝1.2Hz,C)ppm. 13 C NMR (75MHz, CDCl 3 ) δ 15.21 (s, CH 3 ), 20.57 (s, CH 3 ), 22.27 (s, 3CH 3 ), 55.70 (s, C), 57.76 (d, J=13.3 Hz ,CH),65.52(s,CH 2 ),70.54(d,J=5.2Hz,C),125.44(d,J=5.9Hz,CH),125.82(d,J=3.6Hz,CH),126.06( s,CH),126.21(d,J＝5.8Hz,2CH),127.42(s,CH),127.67(s,CH),128.17(s,2CH),128.17(s,2CH),128.51(d,J =4.3Hz,2CH),128.94(s,CH),129.04(s,CH),133.00(s,C),133.41(s,C),137.71(d,J=1.6Hz,C),139.62(d ,J=20.4Hz,C),140.06(s,C),148.43(d,J=22.9Hz,C),154.64(d,J=31.6Hz,C),158.33(s,C),165.04(d ,J=1.2Hz,C)ppm.
应用例Application example
本发明化合物的应用:The application of the compound of the present invention:
选用二苯乙烯甲酮衍生物作为缺电子的烯烃，实现了银催化的基于azomethineylides的1,3-偶极环加成反应。当使用比较传统的手性配体BINAP与银络合形成的中心金属催化剂催化这个不对称反应时，此反应能够顺利的进行，但是得到很低的ee值(2％ee)。当使用本发明设计合成的磷手性中心手性P,O配体时，通过对银催化剂，配体上不同取代基团，溶剂，催化剂与配体的比例和反应温度等条件的优化，发现使用AgNTf2作为催化剂，II’-e作为配体时效果最好。得到最优反应条件以后，通过对反应底物上各个位置取代基的改变，进一步研究此类反应的底物适用性，能够以很高的产率，非对映选择性以及立体选择性得到相应的螺环化合物。A silver-catalyzed azomethineylides-based 1,3-dipolar cycloaddition was achieved by using stilbene ketone derivatives as electron-deficient alkenes. When this asymmetric reaction is catalyzed by the more traditional chiral ligand BINAP complexed with silver, the asymmetric reaction can proceed smoothly, but a very low ee value (2% ee) is obtained. When using the phosphorus chiral center chiral P, O ligand designed and synthesized by the present invention, through the optimization of silver catalyst, different substituent groups on the ligand, solvent, ratio of catalyst to ligand and reaction temperature, it is found that The best results were obtained when AgNTf2 was used as the catalyst and II'-e was used as the ligand. After obtaining the optimal reaction conditions, by changing the substituents at various positions on the reaction substrate, the substrate applicability of this type of reaction can be further studied, and the corresponding reaction can be obtained with high yield, diastereoselectivity and stereoselectivity. of spiro compounds.
表一：拓展试验a Table 1 : Extended Experimenta
a7(0.1mmol),8a(0.2mmol),Ag(I)(0.005mmol),ligand(0.01mmol),Et3N(0.02mmol),DCM(2.0mL),-78℃,24h in a sealed tube.bIsolated Yield.cThe ervalues were determined by chiral HPLC analysis.。 a 7 (0.1mmol), 8a (0.2mmol), Ag(I) (0.005mmol), ligand (0.01mmol), Et 3 N (0.02mmol), DCM (2.0mL),-78 ℃, 24h in a sealed tube. b Isolated Yield. c The ervalues were determined by chiral HPLC analysis.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811293427.XA CN109232650B (en) | 2018-11-01 | 2018-11-01 | Chiral 1-phospha norbornadiene derivatives and synthetic methods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811293427.XA CN109232650B (en) | 2018-11-01 | 2018-11-01 | Chiral 1-phospha norbornadiene derivatives and synthetic methods thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109232650A CN109232650A (en) | 2019-01-18 |
| CN109232650B true CN109232650B (en) | 2020-09-01 |
Family
ID=65080184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811293427.XA Expired - Fee Related CN109232650B (en) | 2018-11-01 | 2018-11-01 | Chiral 1-phospha norbornadiene derivatives and synthetic methods thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109232650B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341476A (en) * | 2020-11-16 | 2021-02-09 | 郑州大学 | High-enantioselectivity 7-thia-2-azaspiro [4.5] decane compound and synthesis method thereof |
| CN112851710B (en) * | 2021-01-07 | 2022-08-23 | 郑州大学 | 1-phospha norbornene chiral phosphine catalyst, and synthesis method and application thereof |
| CN115073521A (en) * | 2022-05-17 | 2022-09-20 | 郑州大学 | 1-phospha norbornene-oxazole chiral phosphine ligand, synthetic method and application thereof, and monocyclic compound |
-
2018
- 2018-11-01 CN CN201811293427.XA patent/CN109232650B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Asymmetric Synthesis of Spirocyclohexanone-Pyrrolidine via Ag(I)-Catalysed Asymmetric 1,3-Dipolar Cycloaddition of Azomethine Ylides;Bdiri B et al;《Tetrahedron: Asymmetry.》;20171231;第28卷;第1044-1052页 * |
| 磷手性中心双膦配体的设计与合成;王越等;《河南省化学会2018年学术年会摘要集》;20180930;第111-112页 * |
| 磷杂环戊二烯[1,5]-σ 键迁移的新进展;王丽丽等;《有机化学》;20131231;第33卷;第33,36-45页 * |
| 磷杂环戊二烯合成结构独特磷配体催化剂;陈美凤等;《上海化工》;20101231;第35卷;第28-31页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109232650A (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109232650B (en) | Chiral 1-phospha norbornadiene derivatives and synthetic methods thereof | |
| Genin et al. | Rh-catalyzed addition of boronic acids to alkynes for the synthesis of trisubstituted alkenes in a biphasic system-Mechanistic study and recycling of the Rh/m-TPPTC catalyst | |
| CN101012187A (en) | Chiral diene ligand, synthesis method and its application in asymmetric reaction | |
| CN101845056B (en) | A Class of C1 Symmetric Chiral Diene Ligands, Synthetic Methods and Their Applications in Asymmetric Reactions | |
| CN109503645B (en) | A kind of chiral geminal disilyl alkane compound containing four silicon-hydrogen bonds and its synthesis method and application | |
| CN107954962B (en) | A kind of preparation method of 4,4-dihalogenated tetrahydropyran | |
| CN110026244B (en) | Alpha alkylation catalyst of nitrile and its application | |
| CN112047839B (en) | 1-iodine-3-perfluoroalkyl alkene compound and preparation method thereof | |
| CN112851710B (en) | 1-phospha norbornene chiral phosphine catalyst, and synthesis method and application thereof | |
| CN103553931A (en) | Method for synthesizing chiral diketone compound | |
| CN111217847B (en) | A kind of thiosilane ligand, its preparation method and application in aryl boronation catalytic reaction | |
| CN109734571B (en) | Method for synthesizing alpha-F-beta-OH-carbonyl compound | |
| Terashima et al. | Syntheses of α-CF 3-α-quaternary ketones via p-quinone methides and their derivatization to compounds with successively congested stereogenic centers | |
| Cheng et al. | Copper-catalyzed asymmetric 1, 3-dipolar cycloaddition of azomethine ylides with β-trifluoromethyl-substituted alkenyl heteroarenes | |
| CN112430228B (en) | A kind of chiral 2,3-dihydrobenzo[b]thiophene 1,1-dioxide, derivative and preparation method | |
| CN110437277B (en) | A kind of synthetic method of phosphoenyl ester compound | |
| Okamatsu et al. | Unique tripodal chiral tertiary amine, 2, 6-trans-1, 2, 6-trisubstituted piperidine with pyridine and bis (phenol) donor groups: Its stereoselective coordination to titanium (IV) ion | |
| CN107400036A (en) | A kind of method of synthesis 1,2- dimethylene cyclobutane chipal compounds | |
| CN104945434A (en) | (2-disubstituted phosphino-phenyl)-1-alkyl-indol-phosphine ligand and synthetic method and application thereof | |
| US6211386B1 (en) | Process for asymmetric hydrogenation | |
| CN106366069B (en) | A kind of preparation method of N- heteroaryl carbazole compound | |
| CN110256350B (en) | Pyrazole ligand, zero-dimensional functional complex, preparation method and application thereof | |
| CN112094182B (en) | A kind of green synthesis method of pharmaceutical intermediate benzocyclohexanone compound | |
| CN114014869B (en) | Chiral 2,2' -bipyridine ligand and preparation method and application thereof | |
| CN104513274A (en) | P chiral pincer compound and palladium coordination compound thereof |
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: 20200901 Termination date: 20211101 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |