CN108069835A - 一种具有联萘酚结构的手性螺烯及其制备方法 - Google Patents
一种具有联萘酚结构的手性螺烯及其制备方法 Download PDFInfo
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- UOYPNWSDSPYOSN-UHFFFAOYSA-N hexahelicene Chemical compound C1=CC=CC2=C(C=3C(=CC=C4C=CC=5C(C=34)=CC=CC=5)C=C3)C3=CC=C21 UOYPNWSDSPYOSN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 10
- -1 binaphthyl phenolic aldehyde Chemical class 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005557 chiral recognition Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 238000006772 olefination reaction Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UTDNEXXRMLOWSU-UHFFFAOYSA-N 2-(methoxymethoxy)naphthalene Chemical compound C1=CC=CC2=CC(OCOC)=CC=C21 UTDNEXXRMLOWSU-UHFFFAOYSA-N 0.000 description 3
- 0 CCc1ccc(C*)c(Br)c1 Chemical compound CCc1ccc(C*)c(Br)c1 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical class BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- ZADYHNRFHQXTOH-UHFFFAOYSA-N heptahelicene Chemical compound C1=CC=C2C3=C(C=4C(=CC=C5C=CC=6C(C=45)=CC=CC=6)C=C4)C4=CC=C3C=CC2=C1 ZADYHNRFHQXTOH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 1
- ZIQKXEDKRUBRKP-UHFFFAOYSA-N C=P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.Br Chemical class C=P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.Br ZIQKXEDKRUBRKP-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKPCLJPYZMKPHM-UHFFFAOYSA-N pentahelicene Chemical compound C1=CC=C2C3=C4C5=CC=CC=C5C=CC4=CC=C3C=CC2=C1 JKPCLJPYZMKPHM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
- B01J31/0232—Halogen-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0228
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/40—Halogenated derivatives with at least one hydroxy group on a condensed ring system containing more than two rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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- 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
Abstract
本发明公开了一种具有联萘酚结构的手性螺烯。本发明还提供了一种手性螺烯的制备方法，该方法以手性联萘酚醛为原料，通过烯烃化和光催化关环合成手性螺烯。本方法具有原料易得，合成方法简单，以及合成路线短等优点。所得手性螺烯化合物可应用于不对称催化或者手性识别领域。
Description
【技术领域】
本发明涉及一种具有联萘酚结构的手性螺烯及其制备方法，属于手性催化剂的设计合成领域。
【背景技术】
螺烯是一类由多个苯环经邻位稠合形成的分子。螺烯具有独特的螺旋结构和手性光学性能，在不对称催化(Angew.Chem.,Int.Ed.,2014,53,861)、分子识别(J.Am.Chem.Soc.,2010,132,3778)、自组装(Angew.Chem.,Int.Ed.,2009,48,7837)、非线性光学材料(Science,1998,282,913)、手性光学材料(J.Am.Chem.Soc.,2014,136,10826；J.Am.Chem.Soc.,2014,136,13045)等领域具有广泛的应用。目前手性螺烯的制备主要依赖于手性色谱柱对外消旋螺烯样品的拆分，直接制备手性螺烯的合成方法比较少。文献中报道，以手性炔化合物(Angew.Chem.,Int.Ed.,2012,51,5857)或者手性醇化合物(J.Am.Chem.Soc.,2015,137,8469)为前体，在过渡金属催化下，可制备手性[5]、[6]或者[7]螺烯。这种方法需要用到昂贵的金属催化剂，而且前体化合物的合成路线复杂，不利于手性螺烯的大量制备和应用。因此，开发新型的简便高效合成手性螺烯的方法具有十分重要的意义。
【发明内容】
本发明所要解决的技术问题在于提供一种具有联萘酚结构的手性螺烯的制备方法。
本发明通过以下技术方案来实现：
一类具有联萘酚结构的手性[6]螺烯，其结构式如式I和式II所示：
式I中，R1为氢、烷基、烷氧基、氯、溴中的至少一种；R2为氢、烷基、烷氧烷基中的至少一种。式II中，R1为氢、烷基、烷氧基、氯、溴中的至少一种；R2为氢、烷基、烷氧烷基中的至少一种。
作为优选，所述结构式中R1为Br。
作为优选，所述结构式中R2为甲氧基甲基。
一类具有联萘酚结构的手性[7]螺烯化合物，其结构式如式III所示：
式III中，R1为氢、烷基、烷氧基、氯、溴中的至少一种；R2为氢、烷基、烷氧烷基中的至少一种。
作为优选，所述结构式中R1为Br。
作为优选，所述结构式中R2为甲氧基甲基。
上述具有联萘酚结构的手性[6]螺烯化合物的制备方法如下，其制备反应式为：
具体包括以下步骤：
a、将手性3-甲酰基联萘酚醚与芳基取代亚甲基三苯基溴化膦于20-80℃下反应1-48小时生成相应的3-芳基取代乙烯基联萘酚醚；
b、所得到的3-芳基取代乙烯基联萘酚醚与光照条件下，于20-80℃下反应2-24小时即可得到具有联萘酚结构的手性[6]螺烯化合物。
上述具有联萘酚结构的手性[7]螺烯化合物的制备方法如下，其制备反应式为：
a、将手性3-甲酰基联萘酚醚与芳基取代双亚甲基三苯基溴化膦于20-80℃下反应1-48小时生成相应的3-芳基取代乙烯基双联萘酚醚；
b、所得到的3-芳基取代乙烯基双联萘酚醚与光照条件下，于20-80℃下反应2-24小时即可得到具有联萘酚结构的手性[7]螺烯化合物。
本发明所述手性螺烯在手性识别和/或手性催化领域中的应用。
本发明提供了一种以手性联萘酚为原料，通过烯烃化反应和光催化关环合成手性[6]螺烯和[7]螺烯的方法。本方法具有原料易得，合成方法简单，以及合成路线短等优点。经仪器检测，所得化合物结构正确。本发明中的手性螺烯利用联萘酚轴手性诱导得到螺烯的螺旋手性，同时保留了联萘酚的羟基催化位点，从而可以实现轴手性和螺旋手性共催化模式，达到良好的不对称催化或者不对称识别效果，可应用于手性催化、手性识别以及手性组装等领域。
【附图说明】
图1为实施例1制备所得手性[6]螺烯化合物A的核磁氢谱图。
图2为实施例1制备所得手性[6]螺烯化合物B的核磁氢谱图。
图3为实施例2制备所得手性[7]螺烯化合物的核磁氢谱图。
【具体实施方式】
下面结合具体实施例对本发明作进一步说明，但本发明并不限于以下实施例。
实施例1：5-(2-(甲氧基甲氧基)萘-1-基)-6-甲氧基甲氧基-15-溴[6]螺烯的制备
a、中间体3-(4-(4-溴苯乙烯基)苯乙烯基)-2,2'-双(甲氧基甲氧基)-1,1'-联萘的合成
将0.2g(R)-2,2'-双(甲氧基甲氧基)-[1,1'-联萘]-3-醛和0.32g(E)-(4-(4-溴苯乙烯基)苄基)三苯基溴化膦(1.05eq.)加入到15mL干燥的THF中，冰浴条件下分批加入叔丁醇钠(1.5eq.)，溶液变为橙红色。冰浴搅拌，半小时后，室温搅拌至反应完全。向反应溶液中加入20mL水淬灭反应，水相用20mL二氯甲烷萃取，有机相用20mL饱和食盐水洗涤,无水硫酸钠干燥，旋去溶剂，得到黄色固体，产率89％。
b、目标物5-(2-(甲氧基甲氧基)萘-1-基)-6-甲氧基甲氧基-15-溴[6]螺烯的合成
将0.1g 3-(4-(4-溴苯乙烯基)苯乙烯基)-2,2'-双(甲氧基甲氧基)-1,1'-联萘，0.077g碘(2eq.)，7.3mL环氧丙烷(715eq.)和170mL甲苯加入反应容器中，容器用橡胶塞密封。向反应溶液中通入氩气，20分钟后用500W汞灯照射反应6h。反应结束后，反应溶液用30mL饱和硫代硫酸钠溶液洗涤，无水硫酸钠干燥，旋蒸，回收甲苯，得到油状物。通过柱层析提纯最后分别得到产物A和产物B(比例为2：1)，总收率68％。
产物A的结构检测结果如下：
1H NMR(500MHz,CDCl3)δ8.51(d,J＝8.3Hz,1H),8.13–8.05(m,3H),8.02(dd,J＝8.5,4.3Hz,2H),7.98(d,J＝8.5Hz,1H),7.93(d,J＝8.2Hz,1H),7.89(d,J＝8.5Hz,1H),7.80(d,J＝8.4Hz,1H),7.70(d,J＝8.4Hz,1H),7.66–7.59(m,2H),7.43(t,J＝7.4Hz,1H),7.34(dd,J＝13.0,4.7Hz,2H),7.24(s,1H),7.04(t,J＝7.4Hz,1H),6.63(t,J＝7.6Hz,1H),5.17(d,J＝7.0Hz,1H),5.00(t,J＝6.1Hz,2H),4.89(d,J＝5.6Hz,1H),3.07(s,3H),2.89(s,3H).
13C NMR(126MHz,CDCl3)δ155.50,151.86,136.81,135.74,134.68,134.14,133.52,132.94,132.75,132.26,131.67,131.51,131.10,130.32,130.21,129.88,129.70,129.58,129.26,129.14,128.66,128.54,126.76,126.26,124.68,123.54,121.69,119.36,102.22,97.48,59.20,58.33.
HRMS(ESI):calcd.for C40H29O4BrNa[M+Na]+:675.11414，found:675.11259.
ee％：98％。光学纯度检测方法：CHIRALPAK IG,n-Hexane/Ethanol/Trifluoroacetic Acid＝95/5/0.1，保留时间：9.209。
[α]D 25＝-1685(c＝0.48,CH2Cl2)。
由上述检测结果可知，该化合物结构正确。
产物B的结构检测结果如下：
1H NMR(500MHz,CDCl3)δ8.58(d,J＝8.4Hz,1H),8.13(d,J＝8.4Hz,1H),8.11(d,J＝8.2Hz,1H),8.07–8.02(m,3H),8.01(d,J＝8.6Hz,1H),7.92(d,J＝8.5Hz,2H),7.77(d,J＝9.1Hz,1H),7.73(d,J＝8.5Hz,1H),7.68(d,J＝8.4Hz,1H),7.42–7.33(m,2H),7.31(s,1H),7.25(t,J＝7.4Hz,1H),7.19(d,J＝8.6Hz,1H),7.06(t,J＝7.3Hz,1H),6.65(t,J＝7.2Hz,1H),5.38–5.25(m,2H),5.09(d,J＝5.4Hz,1H),4.88(d,J＝5.4Hz,1H),3.50(s,3H),3.04(s,3H).
13C NMR(126MHz,CDCl3)δ155.85,151.57,136.42,135.86,134.80,134.20,133.78,132.89,132.73,132.28,132.07,131.62,131.48,131.09,130.55,130.29,130.07,129.82,129.65,129.30,129.09,128.58,128.32,128.00,126.82,126.47,126.30,126.04,124.82,123.01,121.67,119.03,102.14,97.50,59.39,58.56.
HRMS(ESI):calcd.for C40H29O4BrNa[M+Na]+:675.11414，found:675.11295.
ee％：>99％。光学纯度检测方法：CHIRALPAK IA,n-Hexane/Isopropyl Alcohol/Trifluoroacetic Acid＝98/2/0.1，保留时间：5.793。
[α]D 25＝-1738(c＝0.23,CH2Cl2)。
由上述检测结果可知，该化合物结构正确。
实施例2：6,13-双(甲氧基甲氧基)-5,14-双(2-(甲氧基甲氧基)萘-1-基)-9-溴-[7]螺烯的制备
a、中间体1,4-双(2-(2,2'-双(甲氧基甲氧基)-[1,1'-联萘]-3-基)乙烯基)-2-溴苯的合成
将0.3g(R)-2,2'-双(甲氧基甲氧基)-[1,1'-联萘]-3-醛和0.35g((2-溴-1,4-亚苯基)双(亚甲基))双三苯基溴化膦(0.55eq.)加入15mL干燥的THF中。冰浴下，分批加入叔丁醇钠(2.5eq.)，溶液变为橙红色。冰浴下，搅拌半小时，升至室温搅拌至反应完全。向反应溶液中加入20mL水淬灭反应，水相用20mL二氯甲烷萃取，有机相用20mL饱和食盐水洗涤,无水硫酸钠干燥，旋去溶剂，得到黄色固体，产率91％。
b、目标物6,13-双羟基-5,14-双(2-萘酚-1-基)-9-溴-[7]螺烯的合成
将0.1g 1,4-双(2-(2,2'-双(甲氧基甲氧基)-[1,1'-联萘]-3-基)乙烯基)-2-溴苯，0.053g碘(2eq.)，5mL环氧丙烷(715eq.)和170mL甲苯加入反应容器中，容器用橡胶塞密封。向反应溶液中通入氩气，20分钟后用500W汞灯照射反应2h。反应结束后，反应溶液用100mL饱和硫代硫酸钠溶液洗涤，无水硫酸钠干燥，旋蒸，回收甲苯，得到油状物。通过柱层析提纯得黄色固体。
将所得产品溶于THF中，冰浴下,滴加1mL浓盐酸，搅拌半小时，升温至30℃，反应至完全。反应溶液用20mL二氯甲烷萃取，有机相依次用20mL饱和碳酸氢钠溶液和20mL氯化钠溶液洗涤，无水硫酸钠干燥，旋去溶剂，过柱提纯得白色产物，产率35％。
该化合物的结构检测结果如下：
1H NMR(500MHz,CDCl3)δ8.66-8.59(m,2H),8.57(d,J＝8.5Hz,1H),8.51(s,1H),8.09(d,J＝8.6Hz,1H),7.99(d,J＝9.0Hz,2H),7.91(d,J＝8.1Hz,2H),7.38(ddd,J＝13.8,8.9,5.9Hz,6H),7.25(t,J＝7.6Hz,2H),7.04-6.91(m,4H),6.77(d,J＝8.2Hz,2H),6.63(t,J＝7.6Hz,2H),5.46(s,1H),5.44(s,1H),4.86(s,1H),4.85(s,1H).
13C NMR(126MHz,CDCl3)δ153.26,148.99,148.87,132.79,131.54,131.22,130.70,130.57,130.28,129.37,128.59,127.69,126.98,126.70,126.49,126.29,125.97,124.66,124.03,123.92,123.69,122.88,122.08,121.02,120.95,117.84,110.37,110.29,108.39,107.96.
HRMS(ESI):calcd.for C50H28O4Br[M-H]-:771.11765，found:771.11939.
ee％：>99％。光学纯度检测方法：CHIRALPAK IG,n-Hexane/Ethanol/Trifluoroacetic Acid＝75/25/0.1，保留时间：6.816。
[α]D 25＝-1801(c＝0.08,CH2Cl2)。
由上述检测结果可知，该化合物结构正确。
以上所述仅为本发明的优选实施例，对本发明而言，仅仅是说明性的，而非限制性的；本领域普通技术人员的理解，在本发明专利要求所限定的范围内，可对其进行许多改变、修改，甚至等效变更，但都将落入本发明的保护范围。
Claims (6)
1.一类具有联萘酚结构的手性[6]螺烯，其结构式如式I和式II所示：
式I中，R1为氢、烷基、烷氧基、氯、溴中的至少一种；R2为氢、烷基、烷氧烷基中的至少一种。式II中，R1为氢、烷基、烷氧基、氯、溴中的至少一种；R2为氢、烷基、烷氧烷基中的至少一种。
2.一类具有联萘酚结构的手性[7]螺烯化合物，其结构式如式III所示：
式III中，R1为氢、烷基、烷氧基、氯、溴中的至少一种；R2为氢、烷基、烷氧烷基中的至少一种。
3.根据权利要求1中所述的具有联萘酚结构的手性[6]螺烯化合物，其特征在于：所述结构式中R1为氢、烷基、烷氧基、氯、溴中的任意一种。
4.根据权利要求1中所述的具有联萘酚结构的手性[6]螺烯化合物，其特征在于：所述结构式中R2为氢、烷基、烷氧烷基中的任意一种。
5.根据权利要求2中所述的具有联萘酚结构的手性[7]螺烯化合物，其特征在于：所述结构式中R1为氢、烷基、烷氧基、氯、溴中的任意一种。
6.根据权利要求2中所述的具有联萘酚结构的手性[7]螺烯化合物，其特征在于：所述结构式中R2为氢、烷基、烷氧烷基中的任意一种。
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