JP2015510490A - 極大細孔開口を有する金属有機フレームワーク - Google Patents
極大細孔開口を有する金属有機フレームワーク Download PDFInfo
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- JP2015510490A JP2015510490A JP2014535902A JP2014535902A JP2015510490A JP 2015510490 A JP2015510490 A JP 2015510490A JP 2014535902 A JP2014535902 A JP 2014535902A JP 2014535902 A JP2014535902 A JP 2014535902A JP 2015510490 A JP2015510490 A JP 2015510490A
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- Prior art keywords
- irmof
- substituted
- mof
- alkenyl
- alkynyl
- 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.)
- Granted
Links
- 239000012621 metal-organic framework Substances 0.000 title abstract description 57
- 239000011148 porous material Substances 0.000 title description 99
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims description 77
- 125000001072 heteroaryl group Chemical group 0.000 claims description 71
- 125000000623 heterocyclic group Chemical group 0.000 claims description 68
- 125000003342 alkenyl group Chemical group 0.000 claims description 65
- 125000000304 alkynyl group Chemical group 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 59
- 239000002184 metal Substances 0.000 claims description 59
- 125000003118 aryl group Chemical group 0.000 claims description 44
- 125000005647 linker group Chemical group 0.000 claims description 44
- 239000000376 reactant Substances 0.000 claims description 40
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000001179 sorption measurement Methods 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 125000005842 heteroatom Chemical group 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 150000002905 orthoesters Chemical class 0.000 claims description 7
- 125000003107 substituted aryl group Chemical group 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001241 acetals Chemical class 0.000 claims description 6
- 150000002373 hemiacetals Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
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- 238000004519 manufacturing process Methods 0.000 claims description 5
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
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- 229940079593 drug Drugs 0.000 claims 1
- 239000013254 iso-reticular metal–organic framework Substances 0.000 abstract description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 94
- 230000015572 biosynthetic process Effects 0.000 description 87
- 238000003786 synthesis reaction Methods 0.000 description 87
- 239000011777 magnesium Substances 0.000 description 74
- 125000004429 atom Chemical group 0.000 description 67
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 60
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- 239000013078 crystal Substances 0.000 description 56
- -1 R 13 is FG Chemical group 0.000 description 54
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- 150000001875 compounds Chemical class 0.000 description 54
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 239000011541 reaction mixture Substances 0.000 description 46
- 239000007787 solid Substances 0.000 description 45
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- 239000000843 powder Substances 0.000 description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 35
- 125000000524 functional group Chemical group 0.000 description 35
- 239000000523 sample Substances 0.000 description 34
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000047 product Substances 0.000 description 30
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 27
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- 239000003446 ligand Substances 0.000 description 27
- 239000013213 metal-organic polyhedra Substances 0.000 description 27
- 238000005481 NMR spectroscopy Methods 0.000 description 26
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 26
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- 125000004430 oxygen atom Chemical group O* 0.000 description 23
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 22
- 235000019439 ethyl acetate Nutrition 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 229910002666 PdCl2 Inorganic materials 0.000 description 19
- 150000002430 hydrocarbons Chemical class 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 19
- 239000000377 silicon dioxide Substances 0.000 description 19
- 238000004440 column chromatography Methods 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 18
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 18
- 238000001144 powder X-ray diffraction data Methods 0.000 description 18
- 239000002585 base Substances 0.000 description 17
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- 230000007423 decrease Effects 0.000 description 17
- 238000005259 measurement Methods 0.000 description 17
- 150000002739 metals Chemical class 0.000 description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 238000010992 reflux Methods 0.000 description 17
- 229910052682 stishovite Inorganic materials 0.000 description 17
- 229910052905 tridymite Inorganic materials 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- 239000004215 Carbon black (E152) Substances 0.000 description 16
- 238000002835 absorbance Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 16
- 239000012074 organic phase Substances 0.000 description 16
- 101150003085 Pdcl gene Proteins 0.000 description 15
- 150000004696 coordination complex Chemical class 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 15
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 14
- 102000036675 Myoglobin Human genes 0.000 description 14
- 108010062374 Myoglobin Proteins 0.000 description 14
- 239000012043 crude product Substances 0.000 description 14
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 14
- 238000003795 desorption Methods 0.000 description 13
- 238000000921 elemental analysis Methods 0.000 description 13
- 230000006870 function Effects 0.000 description 13
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
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- 238000004729 solvothermal method Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 11
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- 238000010512 small scale reaction Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
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- QENIALCDPFDFHX-UHFFFAOYSA-N 1,4-dibromo-2,5-dimethylbenzene Chemical group CC1=CC(Br)=C(C)C=C1Br QENIALCDPFDFHX-UHFFFAOYSA-N 0.000 description 9
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
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- 229910052698 phosphorus Inorganic materials 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
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- 238000001914 filtration Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
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- RALSHULUKOIMGU-UHFFFAOYSA-N 1,4-dihexyl-2,5-diiodobenzene Chemical compound CCCCCCC1=CC(I)=C(CCCCCC)C=C1I RALSHULUKOIMGU-UHFFFAOYSA-N 0.000 description 7
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000003039 tetrahydroisoquinolinyl group Chemical group C1(NCCC2=CC=CC=C12)* 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000147 tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- XSROQCDVUIHRSI-UHFFFAOYSA-N thietane Chemical compound C1CSC1 XSROQCDVUIHRSI-UHFFFAOYSA-N 0.000 description 1
- 125000002053 thietanyl group Chemical group 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 125000005309 thioalkoxy group Chemical group 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- LWLOKSXSAUHTJO-IMJSIDKUSA-N trans-2,3-butylene carbonate Chemical compound C[C@@H]1OC(=O)O[C@H]1C LWLOKSXSAUHTJO-IMJSIDKUSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- NQPHMXWPDCSHTE-UHFFFAOYSA-N trifluoromethanesulfonyl azide Chemical compound FC(F)(F)S(=O)(=O)N=[N+]=[N-] NQPHMXWPDCSHTE-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000000836 variable-temperature nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- SFYBRCJPMDQKHA-UHFFFAOYSA-N zinc;dinitrate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SFYBRCJPMDQKHA-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本出願は、その開示が本明細書に参照により組み込まれている、2011年10月13日に出願した、米国仮出願番号第61/547,031号の優先権を主張する。
本発明は、Grant No. FG02-08ER15935の元で米国エネルギー省(U.S. Department of Energy)から与えられた政府支援金、及びGrant No. W911NF-06-1-0405の元で米国陸軍(U.S. Army)から与えられた政府支援金を用いて作成された。政府は、本発明において特定の権利を有する。
A1〜A8は、独立して、N又はCのいずれかであり、
X1及びX2はFGであり、
R1〜R12は、独立して、H、FG、(C1〜C12)アルキル、置換(C1〜C12)アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、(C1〜C12)シクロアルキル、置換(C1〜C12)シクロアルキル、アリール、置換アリール、ヘテロ環、置換ヘテロ環、-C(R13)3、-CH(R13)2、-CH2R13、-C(R13)3、-CH(R14)2、-CH2R14、-OC(R13)3、-OCH(R13)2、-OCH2R14、-OC(R14)3、-OCH(R14)2、-OCH2R14、
R1及びR2は、一緒に連結することによって、シクロアルキル、アリール及びヘテロ環を含む群から選択される置換又は非置換の環を形成し、R3及びR4は、一緒に連結することによって、シクロアルキル、アリール及びヘテロ環を含む群から選択される置換又は非置換の環を形成し、
R13は、FG、(C1〜C12)アルキル、(C1〜C12)置換アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、ヘミアセタール、ヘミケタール、アセタール、ケタール、及びオルトエステルを含む群から選択され、
R14は、シクロアルキル、アリール、及びヘテロ環を含む群から選択される1つ以上の置換又は非置換の環であり、
yは、0〜3の数であり、
zは、0〜20の数であり、
ただし、NであるAと結合している場合、Rは不在であることを条件とする)
の連結部分である]を含むMOF又はIRMOFを提供する。一実施形態では、Mは、遷移金属又はアルカリ土類金属のいずれかである。例えば、MはMg又はZnのいずれかである。別の実施形態では、X1及びX2はカルボン酸である。さらなる実施形態では、A1〜A8はCである。前述の実施形態のうちのいずれかのさらなる実施形態では、R1〜R10はヒドロキシルであり、R2〜R5、R7、R9、R11及びR12は水素であり、R6及びR8は、(C1〜C12)アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、及び置換ヘテロ-(C1〜C12)アルキニルからなる群から選択される。またさらなる実施形態では、R6及びR8は(C1〜C6)アルキルである。さらなる実施形態では、zは1〜15の数である。別の実施形態では、MOF又はIRMOFは、ポスト-フレームワーク反応物質をさらに含む。さらなる実施形態では、ポスト-フレームワーク反応物質は、フレームワークの疎水性を低下させる。別の実施形態では、少なくとも1つの連結部分は、式I(a):
A1〜A8は、独立して、N又はCのいずれかであり、
X1及びX2はFGであり、
R1〜R12は、独立して、H、FG、(C1〜C12)アルキル、置換(C1〜C12)アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、(C1〜C12)シクロアルキル、置換(C1〜C12)シクロアルキル、アリール、置換アリール、ヘテロ環、置換ヘテロ環、-C(R13)3、-CH(R13)2、-CH2R13、-C(R13)3、-CH(R14)2、-CH2R14、-OC(R13)3、-OCH(R13)2、-OCH2R14、-OC(R14)3、-OCH(R14)2、-OCH2R14、
R1及びR2は、一緒に連結することによって、シクロアルキル、アリール及びヘテロ環を含む群から選択される置換又は非置換の環を形成し、R3及びR4は、一緒に連結することによって、シクロアルキル、アリール及びヘテロ環を含む群から選択される置換又は非置換の環を形成し、
R13は、FG、(C1〜C12)アルキル、(C1〜C12)置換アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、ヘミアセタール、ヘミケタール、アセタール、ケタール、及びオルトエステルを含む群から選択され、
R14は、シクロアルキル、アリール、及びヘテロ環を含む群から選択される1つ以上の置換又は非置換の環であり、
yは、0〜3の数であり、
zは、0〜20の数であり、
ただし、NであるAと結合している場合、Rは不在であることを条件とする)
の連結部分を含む、高温での反応を含む方法を提供する。
A1〜A8は、独立して、N又はCのいずれかであり、
X1及びX2はFGであり、
R1〜R12は、独立して、H、FG、(C1〜C12)アルキル、置換(C1〜C12)アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、(C1〜C12)シクロアルキル、置換(C1〜C12)シクロアルキル、アリール、置換アリール、ヘテロ環、置換ヘテロ環、-C(R13)3、-CH(R13)2、-CH2R13、-C(R13)3、-CH(R14)2、-CH2R14、-OC(R13)3、-OCH(R13)2、-OCH2R14、-OC(R14)3、-OCH(R14)2、-OCH2R14、
R13は、FG、(C1〜C12)アルキル、(C1〜C12)置換アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、ヘミアセタール、ヘミケタール、アセタール、ケタール、及びオルトエステルを含む群から選択され、
R14は、シクロアルキル、アリール、及びヘテロ環を含む群から選択される1つ以上の置換又は非置換の環であり、
yは、0〜3の数であり、
zは、0〜20の数であり、
ただし、NであるAと結合している場合、Rは不在であることを条件とする)
を含む連結部分から作り出される。
A9〜A14は、独立して、N又はCのいずれかであり、
R53〜R96は、独立して、H、FG、(C1〜C12)アルキル、置換(C1〜C12)アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、(C1〜C12)シクロアルキル、置換(C1〜C12)シクロアルキル、アリール、置換アリール、ヘテロ環、置換ヘテロ環、-C(R13)3、-CH(R13)2、-CH2R13、-C(R13)3、-CH(R14)2、-CH2R14、-OC(R13)3、-OCH(R13)2、-OCH2R14、-OC(R14)3、-OCH(R14)2、-OCH2R14、
R13は、FG、(C1〜C12)アルキル、(C1〜C12)置換アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、ヘミアセタール、ヘミケタール、アセタール、ケタール、及びオルトエステルを含む群から選択され、
R14は、シクロアルキル、アリール、及びヘテロ環を含む群から選択される1つ以上の置換又は非置換の環であり、
yは、0〜3の数であり、
ただし、NであるAと結合している場合、Rは不在であることを条件とする)
を含む連結部分から作り出される。
化合物(3)の合成:還流冷却器を備え、メチル2-(ベンジルオキシ)-4-ヨードベンゾエート(2)(100.2g、0.27mol)、ビス(ピナコラト)ジボロン(76.0g、0.30mol)、KOAc(80.1g、0.82mol)及び(Ph3P)2PdCl2(3.8g、5.4mmol)を充填した、3口丸底フラスコに、無水p-ジオキサン(1.35L)を加えた。室温で、反応混合物を乾燥N2(およそ30分)でパージし、続いてフラスコを予め130℃に温めた油浴に移した。反応混合物を16時間加熱還流してから、室温に冷却し、続いて濾過することによって、不溶性の塩を除去し、これをさらにEtOAcで洗浄した。濾液を真空中で濃縮してから、残渣をEtOAc中に再溶解した。十分な活性炭を通常暗褐色の/黒色の溶液に加え、EtOAc溶液を還流に15分間温めた。セライトのパッドを介した高温濾過で不溶性の物質を除去することによって、通常黄色の溶液を得て、これを真空中で濃縮することによって、油を得た。凝固を促進するため、ヘキサン(200mL)を加え、続いて溶液を真空中で濃縮した。残渣をヘキサンで希釈し、それに続いて真空中で濃縮することをさらに2回繰り返すことによって、残留するあらゆるp-ジオキサン及び/又はEtOAcを除去した。通常、本工程で淡褐色の固体を生成し、これは室温でヘキサン中に不溶性である。ヘキサン(500mL)をこの固体に加え、還流まで温めることによって、均質な溶液を得た。これを、熱供給源から除去し、一晩放置することによって、結晶化した。濾過により、黄色の針状結晶として3を得た(78%、78.1g)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.80 (d, J = 7.5Hz, 1H), 7.53 (d, J = 7.5Hz, 2H), 7.48 (s, 1H), 7.44 (dd, J = 7.5, 1.0Hz, 1H), 7.40 (t, J = 8.0Hz, 2H), 7.31 (t, J = 7.5Hz, 1H), 5.22 (s, 2H), 3.90 (s, 3H), 1.36 (s, 12H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.9, 157.4, 136.9, 134.7 (br.), 130.9, 128.5, 127.7, 127.0, 126.9, 123.1, 119.3, 84.3, 70.6, 52.1, 24.9 ppm. HRMS (ESI) 計算値C21H25B1O5: m/z = 369.1873 ([M + H]+); 実測値m/z = 369.1884; m/z = 391.1693 ([M + Na]+); 実測値m/z = 369.1702.
化合物(6)の合成:ボロン酸エステル3(9.20g、25.0mmol、1.0当量)及びブロミド4(35.9g、135.8mmol、5.4当量)を、脱気した2:1p-ジオキサン/H2O混合物(300mL)中に溶解した。CsF(11.4g、75.0mmol、3.0当量)及びPdCl2(dppf)(1.11g、1.36mmol、5mol%)を加え、これを14時間加熱還流した。反応混合物を室温に冷却してから、CH2Cl2及びH2Oで抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相を乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上に吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン:CH2Cl2=1:1→1:10)で処理することによって、黄色がかった油として化合物6を得た(7.75g、18.2mmol、67%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.87 (d, J = 7.9Hz, 1H), 7.48 (m, 2H), 7.43 (s, 1H), 7.40 (m, 2H), 7.31 (m, 1H), 7.03 (s, 1H), 6.91 (dd, J = 7.9, 1.5Hz, 1H), 6.89 (d, J = 1.3Hz, 1H), 5.21 (s, 2H), 3.93 (s, 3H), 2.38 (s, 3H), 2.08 (s, 3H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.7, 157.8, 146.4, 140.0, 136.6, 135.2, 134.5, 133.9, 131.8, 131.5, 128.6, 127.8, 126.8, 124.2, 121.3, 119.2, 114.9, 70.6, 52.1, 22.3, 19.5 ppm. HRMS (ESI) 計算値C23H22BrO3: m/z = 425.0747 ([M + H]+); 実測値m/z = 425.0755.
化合物(7)の合成:ボロン酸エステル3(1.08g、2.92mmol、1.0当量)及びヨウ化物5(5.40g、11.7mmol、4.0当量)を、脱気したp-ジオキサン(150mL)及びH2O(50mL)中に溶解した。CsF(1.33g、8.76mmol、3.0当量)及びPdCl2(dppf)(120mg、0.147mmol、5mol%)を加え、反応混合物を14時間加熱還流した。次いでこれを室温に冷却してから、CH2Cl2及びH2Oで抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相を乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上で吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=5:1)で処理することによって、無色の固体として化合物7を得た(1.11g、1.93mmol、66%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.90 (d, J = 8.2Hz, 1H), 7.74 (s, 1H), 7.51 (d, J = 8.5Hz, 2H), 7.40 (t, J = 7.6Hz, 2H), 7.32 (t, J = 7.3Hz, 1H), 7.07 (s, 1H), 7.02-7.00 (m, 3H), 6.95 (s, 1H), 5.24 (s, 2H), 3.94 (s, 3H), 2.41 (s, 3H), 2.15 (s, 3H), 2.04 (m, 6H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.8, 147.3, 141.4, 140.2, 139.88, 139.81, 138.5, 136.8, 135.4, 133.2, 132.3, 131.7, 131.3, 130.9, 130.5, 128.6, 127.8, 126.8, 121.6, 118.9, 115.0, 99.6, 70.6, 52.1, 27.5, 19.8, 19.3, 19.0 ppm. HRMS (ESI) 計算値C31H30IO3: m/z = 577.1234 ([M + H]+); 実測値m/z = 577.1229.
化合物(8)の合成:ブロミド6(7.75g、18.2mmol、1.0当量)を、乾燥及び脱気したMe2SO(80mL)中に溶解した。ビス(ピナコレート)ジボロン(5.08g、20.0mmol、1.1当量)、KOAc(5.36g、54.6mmol、3.0当量)及びPdCl2(dppf)(743mg、0.91mmol、5mol%)を加え、これを80℃に14時間加熱した。次いで反応混合物を室温に冷却し、CH2Cl2及びH2Oで抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相をH2Oで洗浄し、乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上に吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=5:1)で処理することによって、無色の油として化合物8を得た(8.04g、17.0mmol、94%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.91 (d, J = 7.8Hz, 1H), 7.68 (s, 1H), 7.51 (m, 2H), 7.41 (m, 2H), 7.33 (m, 1H), 7.02 (s, 1H), 6.98-6.95 (m, 2H), 5.23 (s, 2H), 3.96 (s, 3H), 2.55 (s, 3H), 2.14 (s, 3H), 1.39 (s, 12H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.7, 157.8, 147.4, 143.1, 142.4, 138.1, 136.7, 131.7, 131.3, 130.8, 128.6, 127.8, 126.8, 121.3, 119.0, 114.9, 83.5, 70.6, 52.1, 25.1, 24.9, 21.7, 19.5 ppm. HRMS (ESI) 計算値C29H34BO6: m/z = 472.2544 ([M + H]+); 実測値m/z = 472.2530.
化合物(9)の合成:ヨウ化物7(971mg、1.68mmol、1.0当量)を、乾燥及び脱気したMe2SO(7mL)中に溶解した。ビス(ピナコレート)ジボロン(470mg、1.85mmol、1.1当量)、KOAc(494mg、5.04mmol、3.0当量)及びPdCl2(PPh3)2(69mg、0.084mmol、5mol%)を加え、反応混合物を80℃に15時間加熱した。室温に冷却後、反応混合物をH2O及びCH2Cl2で抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相をH2Oで洗浄し、乾燥させ(MgSO4)、蒸発させ、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=9:1)で処理することによって、無色の発泡体として化合物9を得た(810mg、1.41mmol、84%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.93 (d, J = 8.2Hz, 1H), 7.70 (s, 1H), 7.54 (d, J = 8.0Hz, 2H), 7.42 (t, J = 7.5Hz, 2H), 7.35 (t, J = 7.3Hz, 1H), 7.10 (s, 1H), 7.05 (m, 2H), 6.99 (s, 1H), 6.98 (s, 1H), 5.27 (s, 2H), 3.97 (s, 3H), 2.55 (s, 3H), 2.17 (s, 3H), 2.10 (s, 3H), 2.06 (s, 3H), 1.39 (s, 12H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.8, 147.5, 143.8, 142.0, 141.3, 139.5, 137.4, 136.8, 133.2, 132.1, 132.0, 131.7, 131.2, 130.9, 130.7, 128.6, 127.8, 126.8, 121.7, 118.8, 115.1, 83.5, 70.6, 52.1, 34.7, 31.6, 25.3, 24.98, 24.95, 22.7, 21.8, 20.8, 19.8, 19.3, 19.2, 14.3 ppm. HRMS (ESI) 計算値C37H41BO5: m/z = 576.3156 ([M + H]+); 実測値m/z =
576.3169.
化合物(10)の合成:ボロン酸エステル8(2.60g、5.50mmol、1.0当量)、ヨウ化物5(10.2g、22.1mmol、4.0当量)、及びCsF(2.50g、16.5mmol、3.0当量)を、80℃で、p-ジオキサン(500mL)及びH2O(200mL)の脱気した混合物中に溶解した。次いで、PdCl2(dppf)(225mg、0.276mmol、5mol%)を加え、反応混合物を14時間加熱還流した。室温に冷却後、反応混合物をCH2Cl2(400mL)及びH2O(1000mL)で抽出した。水相をCH2Cl2で2回洗浄した(2×200mL)。合わせた有機相を飽和食塩水で洗浄し、乾燥させ(MgSO4)、蒸発させた。粗生成物を、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=5:1)で処理することによって、無色の油として、生成物10を得た(2.34g、3.44mmol、63%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.94 (d, J = 8.2Hz, 1H), 7.77 (s, 1H), 7.55 (d, J = 7.4Hz, 2H), 7.43 (t, J = 7.6Hz, 2H), 7.35 (t, J = 7.3Hz, 1H), 7.13 (s, 1H), 7.09-7.03 (m, 5H), 6.99 (m, 1H), 5.27 (s, 2H), 3.97 (s, 3H), 2.45 (s, 3H), 2.20 (s, 3H), 2.14-2.06 (m, 12H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.9, 147.5, 141.83, 141.77, 141.20, 141.14, 141.00, 140.1, 139.8, 139.53, 139.50, 139.41, 139.36, 138.39, 138.36, 136.8, 135.56, 135.49, 133.45, 133.39, 132.92, 132.83, 132.66, 132.56, 132.1, 131.66, 131.60, 131.54, 130.78, 130.73, 130.69, 130.62, 130.48, 130.45, 128.6, 127.8, 126.8, 121.7, 118.8, 115.1, 99.4, 70.6, 52.1, 34.70, 34.57, 27.4, 25.3, 20.7, 19.83, 19.79, 19.47, 19.44, 19.37, 19.31, 18.98, 18.85 ppm. HRMS (ESI) 計算値C39H38IO3: m/z = 681.1860 ([M + H]+); 実測値m/z = 681.1848.
化合物(11)の合成:ヨウ化物10(2.06g、3.02mmol、1.0当量)を、乾燥及び脱気したMe2SO(20mL)中に溶解した。ビス(ピナコラト)ジボロン(843mg、3.32mmol、1.1当量)、KOAc(888mg、9.06mmol、3.0当量)及びPdCl2(dppf)(123mg、0.151mmol、5mol%)を加え、これを80℃に14時間加熱した。反応混合物を室温に冷却し、CH2Cl2及びH2Oで抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相をH2Oで洗浄し、乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上に吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=7:1)で処理することによって、無色の固体として、化合物11を得た(1.50g、2.2mmol、72%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.94 (d, J = 8.3Hz, 1H), 7.71 (s, 1H), 7.55 (d, J = 7.7Hz, 2H), 7.44-7.41 (m, 2H), 7.35 (m, 1H), 7.12 (s, 1H), 7.10-6.99 (m, 6H), 5.27 (s, 2H), 3.97 (s, 3H), 2.57 (s, 3H), 2.20 (s, 3H), 2.14-2.06 (m, 12H), 1.39 (s, 12H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.9, 147.6, 144.25, 144.19, 141.95, 141.93, 141.38, 141.31, 140.49, 140.44, 139.87, 139.82, 139.44, 139.41, 137.3, 136.8, 133.52, 133.46, 132.72, 132.65, 132.62, 132.55, 132.19, 132.14, 132.06, 132.04, 131.66, 131.60, 131.04, 130.96, 130.75, 130.61, 130.59, 130.40, 130.38, 128.6, 127.8, 126.8, 121.7, 118.8, 115.11, 115.10, 83.4
, 77.1, 70.6, 52.1, 31.6, 25.06, 24.98, 24.96, 21.76, 21.73, 19.82, 19.78, 19.49, 19.45, 19.36, 19.31, 19.21, 19.08 ppm. HRMS (ESI) 計算値C45H50BO5: m/z = 680.3782 ([M + H]+); 実測値m/z = 680.3776.
化合物(12)の合成:一般的なカップリング手順(4.00gのヨウ化アリールをベースとする)に従い、化合物2及び3を反応させ、所望の生成物を溶液から沈殿させた。二相性溶液の水層(下側)を、シリンジを介して除去し、生成物を残存する暗褐色のp-ジオキサン層の濾過で収集した。収集した生成物をEtOAcで洗浄し、風乾させることによって、オフホワイト色の粉末として12を得た(83%、4.35g)。これは、さらなる精製を必要としなかった。1H NMR (500MHz, CDCl3, 25℃): δ = 7.91 (d, J = 8.0Hz, 2H), 7.52 (d, J = 7.5Hz, 4H), 7.42 (t, J = 7.5Hz, 4H), 7.34 (t, J = 7.5Hz, 2H), 7.16 (dd, J = 8.0, 1.5Hz, 2H), 7.08 (d, J = 1.5Hz, 2H), 5.23 (s, 4H), 3.93 (s, 6H) ppm. 13C NMR (125MHz, CDCl3, 25℃): δ = 166.5, 158.6, 145.4, 136.7, 132.6, 128.8, 128.1, 127.0, 120.2, 119.6, 113.1, 70.9, 52.3 ppm. MS (ESI) 計算値C30H16O6: m/z = 483.2 ([M + H]+), 505.2 ([M + Na]+)及び987.3 ([2M + Na]+; 実測値m/z = 483.4 ([M + H]+), 505.4 ([M + Na]+)及び987.1 ([2M + Na]+).
化合物(13)の合成:一般的なカップリング手順(2.00gのアリールジブロミドをベースとする)に従い、化合物3及び4を反応させ、所望の生成物を溶液から沈殿させた。二相性溶液の水層(下側)を、シリンジを介して除去し、生成物を残存する暗褐色のp-ジオキサン層の濾過で収集した。収集した生成物をEtOAcで洗浄し、風乾させたままにすることによって、オフホワイト色の粉末として13を得た(96%、4.29g)。これは、さらなる精製を必要としなかった。1H NMR (500MHz, THF-d8, 25℃): δ = 7.96 (d, J = 7.5Hz, 2H), 7.66 (d, J = 7.5Hz, 4H), 7.48 (t, J = 7.5Hz, 4H), 7.39 (t, J = 7.5Hz, 2H), 7.24 (s, 2H), 7.22 (s, 2H), 7.10 (dd, J = 8.0, 1.0Hz, 2H), 5.36 (s, 4H), 3.98 (s, 6H), 2.30 (s, 6H) ppm. 13C NMR (125MHz, THF-d8, 25℃): δ = 167.0, 159.3, 148.2, 141.8, 138.8, 133.7, 132.6, 132.6, 129.5, 128.6, 127.9, 122.2, 120.8, 116.1, 71.4, 52.2, 20.3 ppm. MS (ESI) 計算値C38H34O6: m/z = 587.2 ([M + H]+), 609.2 ([M + Na]+)及び1195.5 ([2M + Na]+; 実測値m/z = 587.4 ([M + H]+), 609.5 ([M + Na]+)及び1195.1 ([2M + Na]+).
化合物(14)の合成:ボロン酸エステル3(4.78g、13.0mmol、3.0当量)及びヨウ化物5(2.00g、4.33mmol、1.0当量)を、脱気した2:1p-ジオキサン/H2O混合物(420mL)中に溶解した。CsF(3.95g、26.0mmol、6.0当量)、及びPdCl2(dppf)(354mg、0.433mmol、10mol%)を加え、反応混合物を14時間加熱還流した。これを室温に冷却してから、CH2Cl2及びH2Oで抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相を乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上に吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=5:1)で処理することによって、無色の固体として化合物14を得た(2.60g、3.82mmol、87%)。1H NMR (500MHz, CD2Cl2, 25℃): δ = 7.86 (d, J = 7.9Hz, 2H), 7.51 (m, 4H), 7.40 (m, 4H), 7.33 (m, 2H), 7.13 (m, 2H), 7.06 (d, J = 1.3Hz, 2H), 7.03 (dd, J = 7.9, 1.5Hz, 2H), 7.01 (s, 2H), 5.29 (s, 4H), 3.89 (s, 6H), 2.20 (s, 6H), 2.09 (s, 6H) ppm. 13C NMR (126MHz, CD2Cl2, 25℃): δ = 166.8, 158.2, 147.7, 141.2, 140.0, 137.3, 133.7, 132.6, 131.9, 131.8, 131.2, 128.9, 128.2, 127.4, 121.9, 119.5, 115.4, 71.0, 52.3, 20.0, 19.5 ppm. HRMS (ESI) 計算値C46H43O6: m/z = 691.3051 ([M + H]+); 実測値m/z = 691.3067.
化合物(15)の合成:ボロン酸エステル8(1.77g、3.75mmol、3.0当量)及び1,4-ジヨード-2,5-ジメチルベンゼン(447mg、1.25mmol、1.0当量)を、脱気した2:1p-ジオキサン/H2O混合物(150mL)中に溶解した。CsF(1.14g、7.50mmol、6.0当量)及びPdCl2(dppf)(102mg、0.125mmol、10mol%)を加え、反応混合物を14時間加熱還流した。次いでこれを室温に冷却してから、CH2Cl2及びH2Oで抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相を乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上に吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=5:1)で処理することによって、無色の固体として化合物15を得た(765mg、0.962mmol、77%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.92 (d, J = 8.2Hz, 2H), 7.53 (m, 4H), 7.41 (m, 4H), 7.32 (m, 2H), 7.11 (s, 2H), 7.09 (m, 2H), 7.05-7.03 (m, 6H), 5.25 (s, 4H), 3.95 (s, 6H), 2.19 (s, 6H), 2.13 (s, 3H), 2.12 (s, 3H), 2.11 (m, 6H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.9, 147.6, 141.30, 141.23, 140.03, 139.98, 139.50, 139.47, 136.8, 133.50, 133.44, 132.84, 132.74, 132.10, 132.08, 131.67, 131.60, 130.79, 130.72, 130.70, 128.6, 127.8, 126.8, 121.7, 118.8, 115.11, 115.10, 70.6, 52.1, 19.84, 19.80, 19.51, 19.47, 19.34 ppm. HRMS (ESI) 計算値C54H51O6: m/z = 795.3680 ([M + H]+); 実測値m/z = 795.3659.
化合物(16)の合成:ボロン酸エステル8(600mg、1.27mmol、3.0当量)及びヨウ化物5(196mg、0.423mmol、1.0当量)を、脱気した2:1p-ジオキサン/H2O混合物(45mL)中に溶解した。CsF(386mg、2.54mmol、6.0当量)及びPdCl2(dppf)(35mg、0.043mmol、10mol%)を加え、反応混合物を14時間加熱還流した。これを、室温に冷却してから、CH2Cl2及びH2Oで抽出した。水相を、CH2Cl2で2回洗浄した。合わせた有機相を乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上に吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=5:1)で処理することによって、無色の固体として化合物16を得た(229mg、0.255mmol、60%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.93 (d, J = 8.3Hz, 2H), 7.53 (m, 4H), 7.40 (m, 4H), 7.33( m, 2H), 7.12-7.04 (m, 12H), 5.26 (s, 4H), 3.95 (s, 6H), 2.19 (s, 6H), 2.15-2.12 (m, 18H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.9, 147.6, 141.4, 141.3, 140.8, 140.5, 140.44, 140.43, 140.38, 139.9, 139.83, 139.82, 139.78, 139.7, 139.5, 139.4, 136.81, 136.78, 133.54, 133.48, 133.9, 132.93, 132.88, 132.82, 132.75, 132.72, 132.65, 132.6, 132.08, 132.06, 131.71, 131.67, 131.5, 130.9, 130.83, 130.78, 130.7, 128.6, 127.8, 126.8, 121.7, 118.8, 115.1, 70.6, 52.1, 19.9, 19.8, 19.53, 1949, 19.47, 19.46, 19.38, 19.36 ppm. HRMS (ESI)
計算値C62H59O6: m/z = 899.4306 ([M + H]+); 実測値m/z = 899.4330.
化合物(18)の合成:ボロン酸エステル8(697mg、1.48mmol、2.2eq.)及びヨウ化物17(334mg、0.670mmol、1.0当量)を、p-ジオキサン(15mL)及びH2O(7.5mL)の脱気した混合物中に溶解した。CsF(610mg、4.02mmol、6.0当量)及びPdCl2(dppf)(55mg、0.067mmol、10mol%)を加え、反応混合物を、15時間加熱還流した。これを室温に冷却しH2O及びCH2Cl2で抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相を乾燥させ(MgSO4)、蒸発させた。粗生成物をカラムクロマトグラフィー(SiO2:CH2Cl2:ヘキサン=1:1→1:0)で処理することによって、無色の固体として化合物18を得た(465mg、0.497mmol、74%)。1H-NMR (500MHz; CDCl3): δ = 7.95 (d, J = 8.2Hz, 2H), 7.56 (d, J = 7.5Hz, 4H), 7.44 (t, J = 7.6Hz, 4H), 7.35 (t, J = 7.4Hz, 2H), 7.14 (m, 4H), 7.09-7.06 (m, 6H), 5.28 (s, 4H), 3.98 (s, 6H), 2.49 (m, 2H), 2.40-2.35 (m, 2H), 2.22 (s, 6H), 2.15 (d, J = 3H), 2.14 (s, 3H), 1.48 (m, 4H), 1.22 (m, 12H), 0.85 (t, J = 7.0Hz, 6H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.9, 147.6, 141.34, 141.25, 139.51, 139.49, 139.40, 139.37, 137.41, 137.36, 136.8, 133.64, 133.58, 132.00, 131.93, 131.82, 131.81, 131.66, 130.77, 130.74, 130.06, 130.00, 128.6, 127.8, 126.8, 121.7, 118.8, 115.1, 70.6, 52.1, 32.51, 32.46, 31.6, 30.75, 30.66, 29.00, 28.95, 22.5, 19.85, 19.81, 19.72, 19.58, 14.1 ppm. HRMS (ESI) 計算値C64H71O6: m/z = 935.5245 ([M + H]+); 実測値m/z = 935.5213.
化合物(19)の合成:ボロン酸エステル9(641mg、1.11mmol、2.2当量)及びヨウ化物17(252mg、0.505mmol、1.0当量)をp-ジオキサン(11mL)及びH2O(5.5mL)の脱気した混合物中に溶解した。CsF(460mg、43.03mmol、6.0当量)及びPdCl2(dppf)(41mg、0.050mmol、10mol%)を加え、反応混合物を15時間加熱還流した。これを室温に冷却し、H2O及びCH2Cl2で抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相を乾燥させ(MgSO4)、蒸発させた。粗生成物を、カラムクロマトグラフィー(SiO2:CH2Cl2)で処理することによって、無色の固体として化合物19を得た(527mg、0.460mmol、91%)。1H-NMR (500MHz; CDCl3): δ = 7.95 (d, J = 8.2Hz, 2H), 7.56 (d, J = 7.6Hz, 4H), 7.44 (t, J = 7.6Hz, 4H), 7.35 (t, J = 7.4Hz, 2H), 7.17-7.06 (m, 15H), 5.28 (s, 4H), 3.98 (s, 6H), 2.51 (m, 2H), 2.39 (m, 2H), 2.22 (s, 6H), 2.18 (s, 3H), 2.15-2.12 (m, 15H), 1.50-1.45 (m, 4H), 1.28-1.17 (m, 12H), 0.85 (m, 6H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.9, 147.6, 141.50, 141.40, 140.5, 139.72, 139.64, 139.44, 139.40, 137.56, 137.51, 136.8, 133.55, 133.48, 133.25, 133.20, 133.14, 133.12, 133.02, 132.96, 132.95, 132.45, 132.43, 132.31, 132.09, 132.03, 131.76, 131.67, 131.58, 131.26, 131.21, 131.18, 131.12, 130.77, 130.58, 130.26, 130.17, 130.13, 128.6, 127.8, 126.8, 121.7, 118.8, 115.1, 70.6, 52.1, 32.8, 32.58, 32.53, 31.64, 31.59, 31.48, 31.08, 30.95, 30.85, 30.70, 29.15, 29.10, 29.07, 22.71, 22.58, 22.55, 19.86, 19.79, 19.62, 19.52, 19.49, 19.44, 19.2, 14.16, 14.08 ppm. HRMS (ESI) 計算値C96H103O6: m/z 1350.7676 ([M + H]+); 実測値m/z = 1351.7733.
化合物(20)の合成:ボロン酸エステル11(916mg、1.35mmol、2.2当量)及びヨウ化物17(305mg、0.612mmol、1.0当量)を、p-ジオキサン(18mL)及びH2O(9mL)の脱気した混合物中に溶解した。PdCl2(dppf)(50.0mg、0.061mmol、10mol%)及びCsF(558mg、3.67mmol、6.0当量)を加え、反応混合物を106℃に13時間加熱した。反応混合物を室温に冷却し、沈殿物を濾別し、H2O及びMeOHで洗浄し、真空下で乾燥させ、カラムクロマトグラフィー(SiO2:CH2Cl2)で処理することによって、無色の固体として化合物20を得た(700mg、0.518mmol、85%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.93 (d, J = 8.3Hz, 2H), 7.54 (d, J = 7.2Hz, 4H), 7.42 (t, J = 7.6Hz, 4H), 7.33 (t, J = 7.4Hz, 2H), 7.17-7.10 (m, 12H), 7.07-7.05 (m, 6H), 5.27 (s, 4H), 3.96 (s, 6H), 2.53-2.37 (m, 4H), 2.20 (s, 6H), 2.14 (m, 30H), 1.48 (m, 4H), 1.21 (m, J = 6.7Hz, 12H), 0.88-0.81 (m, 6H) ppm. 13C NMR (126MHz; CDCl3, 25℃): δ = 166.8, 157.9, 147.6, 141.45, 141.39, 140.71, 140.63, 140.56, 140.46, 140.37, 140.28, 140.18, 140.13, 140.09, 140.03, 139.93, 139.90, 139.81, 139.76, 139.70, 139.45, 139.43, 137.63, 137.60, 137.56, 137.54, 137.51, 136.8, 133.56, 133.51, 133.10, 133.05, 132.98, 132.94, 132.88, 132.73, 132.67, 132.64, 132.57, 132.53, 132.45, 132.39, 132.08, 132.06, 131.73, 131.68, 131.22, 131.13, 130.98, 130.95, 130.73, 130.65, 130.35, 130.30, 130.22, 130.17, 130.07, 130.03, 128.6, 127.8, 126.8, 121.7, 118.8, 115.1, 70.6, 52.1, 32.90, 32.85, 32.79, 32.67, 32.62, 32.57, 31.61, 31.49, 31.11, 31.02, 30.98, 30.88, 30.86, 30.72, 29.23, 29.18, 29.15, 29.12, 29.10, 29.05, 22.59, 22.57, 19.85, 19.81, 19.78, 19.76, 19.64, 19.60, 19.55, 19.50, 19.47, 19.40, 19.37, 19.33, 19.28, 14.17, 14.09 ppm. HRMS (ESI) 計算値C96H103O6: m/z = 1351.7749 ([M + H]+); 実測値m/z = 1351.7758.
化合物(21)の合成:ボロン酸エステル9(1.50g、2.61mmol、1.0当量)及びヨウ化物17(5.20g、10.4mmol、4.0当量)を、ジオキサン(100mL)及びH2O(50mL)の脱気した混合物中に80℃で溶解した。PdCl2(dppf)(106mg、0.131mmol、5mol%)及びCsF(1.19g、7.83mmol、3.0当量)を加え、反応混合物を106℃に13時間加熱した。これを室温に冷却し、CH2Cl2及びH2Oで抽出した。水相をCH2Cl2で2回洗浄し、合わせた有機相を乾燥させ(MgSO4)、蒸発させ、シリカゲル上に吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=5:1)で処理することによって、無色の固体として化合物21を得た(856mg、1.04mmol、40%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.94 (d, J = 8.3Hz, 1H), 7.76 (s, 1H), 7.55 (d, J = 7.2Hz, 2H), 7.43 (t, J = 7.6Hz, 2H), 7.35 (t, J = 7.4Hz, 1H), 7.13 (s, 1H), 7.10-7.00 (m, 6H), 5.28 (s, 2H), 3.98 (s, 3H), 2.72 (m, 2H), 2.42 (m, 1H), 2.31 (m, 1H), 2.21 (s, 3H), 2.15-2.11 (m, 6H), 2.06 (m, 3H), 1.46-1.14 (m, 16H), 0.93-0.83 (m, 6H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.9, 147.5, 142.3, 141.39, 141.26, 140.55, 140.52, 140.13, 140.08, 139.61, 139.53, 139.48, 139.36, 139.27, 136.8, 133.45, 133.37, 132.82, 132.67, 132.54, 132.13, 132.07, 131.67, 131.47, 130.90, 130.84, 130.78, 130.69, 130.50, 130.40, 128.6, 127.8, 126.8, 121.7, 118.8, 115.1, 99.2, 70.6, 52.1, 40.38, 40.34, 34.7, 32.4, 32.1, 31.7, 31.45, 31.36, 30.81, 30.66, 30.43, 30.30, 29.15, 29.08, 29.00, 25.3, 22.69, 22.50, 19.84, 19.77, 19.62, 19.47, 19.2, 14.15, 14.06 ppm. HRMS (ESI) 計算値C49H58IO3: m/z = 821.3425 ([M + H]+); 実測値m/z = 821.3424.
化合物(22)の合成:ジブロミド25(1.00g、2.12mmol、1.0当量)、ビス(ピナコラト)ジボロン(1.13g、4.45mmol、2.1当量)、PdCl2(dppf)(173mg、0.212mmol、10mol%)、及びKOAc(1.25g、12.7mmol、6.0当量)を、無水Me2SO(50mL)を含有する炎光乾燥したフラスコに加え、反応混合物を16時間加熱還流した。これを、室温に冷却し、H2O(25mL)に加え、次いで、CH2Cl2で3回抽出した。次いで有機層をH2Oで十分に洗浄した。有機相を乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上に吸収し、カラムクロマトグラフィー(SiO2:ヘキサン)で処理することによって、無色の固体として化合物22を得た(371mg、0.655mmol、31%)。1H NMR (500MHz, CD2Cl2, 25℃): δ = 7.66 (s, 2H), 6.99 (m, 4H), 2.54 (s, 6H), 2.10 (s, 6H), 2.04 (s, 6H), 1.39 (s, 24H) ppm. 13C NMR (126MHz, CD2Cl2, 25℃): δ= 144.5, 142.2, 140.7, 137.7, 132.9, 132.8, 132.4, 131.3, 131.2, 130.7, 83.8, 25.1, 21.80, 21.78, 19.4, 19.3, 19.1 ppm. HRMS (ESI) 計算値C36H49B2O4: m/z = 565.3884 ([M + H]+); 実測値m/z = 565.3864.
化合物(23)の合成:ボロン酸エステル22(151mg、0.266mmol、1.0当量)及びヨウ化物21(480mg、0.585mmol、2.2当量)をジオキサン(12mL)及びH2O(6mL)の脱気した混合物中に懸濁させた。PdCl2(dppf)(22mg、0.0269mmol、10mol%)及びCsF(242mg、1.60mmol、6.0当量)を加え、反応混合物を106℃に15時間加熱した。これを室温に冷却し、沈殿物を濾別し、H2O及びMeOHで洗浄し、真空で乾燥させた。ベージュ色の粗生成物を、カラムクロマトグラフィー(SiO2:CH2Cl2)で処理することによって、無色の固体として、化合物23を生成した(373mg、0.219mmol、82%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.96 (d, J = 8.2Hz, 2H), 7.57 (d, J = 7.6Hz, 4H), 7.44 (t, J = 7.6Hz, 4H), 7.36 (t, J = 7.4Hz, 2H), 7.19-7.07 (m, 22H), 5.29 (s, 4H), 3.99 (s, 6H), 2.54 (m, 4H), 2.41 (m, 4H), 2.23-2.14 (m, 46H), 1.54-1.46 (m, 8H), 1.28-1.17 (m, 24H), 0.87 (m, 12H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.9, 147.6, 141.53, 141.43, 140.68, 140.65, 140.57, 140.47, 140.33, 140.28, 140.21, 140.18, 140.02, 139.99, 139.90, 139.87, 139.78, 139.71, 139.68, 139.63, 139.60, 139.58, 139.45, 139.40, 137.67, 137.64, 137.61, 137.57, 137.54, 137.51, 137.49, 137.46, 137.44, 136.8, 133.57, 133.50, 133.21, 133.15, 133.05, 132.99, 132.87, 132.82, 132.76, 132.71, 132.66, 132.64, 132.60, 132.51, 132.50, 132.45, 132.42, 132.31, 132.09, 132.04, 131.78, 131.68, 131.60, 131.29, 131.24, 131.20, 131.16, 131.11, 130.90, 130.78, 130.71, 130.67, 130.59, 130.37, 130.32, 130.25, 130.19, 130.13, 130.10, 130.06, 130.04, 130.00, 128.6, 127.8, 121.7, 118.8, 115.1, 70.6, 52.1, 34.7, 32.8, 32.62, 32.61, 31.61, 31.50, 31.10, 31.01, 30.97, 30.87, 30.84, 30.72, 29.23, 29.18, 29.14, 29.10, 29.05, 22.60, 22.57, 20.8, 19.87, 19.80, 19.78, 19.64, 19.61, 19.53, 19.50, 19.48, 19.46, 19.37, 19.31, 19.25, 14.17, 14.09 ppm. HRMS (ESI) 計算値C122H139O6: m/z = 1700.0566 ([M + H]+); 実測値m/z = 1700.0582.
化合物(24)の合成:1,4-ジブロモ-2,5-ジメチルベンゼン(4)(25.0g、94.7mmol、1.0当量)、ビス(ピナコラト)ジボロン(50.5g、199mmol、2.1当量)、PdCl2(dppf)(3.87g、4.74mmol、5mol%)、及びKOAc(55.8g、568mmol、6.0当量)を、無水Me2SO(300mL)を含有する炎光乾燥したフラスコに加えた。反応混合物を16時間加熱還流した。次いで、これを室温に冷却し、H2O(100mL)に加えてからCH2Cl2で3回抽出した。次いで有機層をH2Oで十分に洗浄した。有機相を乾燥させ(MgSO4)、濾過し、蒸発させた。EtOAc(250mL)を、活性炭(10g)と共に粗製の混合物に加え、反応混合物を3時間還流させた。これを室温に冷却し、セライトを介して濾過し、セライトをCH2Cl2で十分に洗浄した。CH2Cl2層を蒸発させて、生成物がEtOAcから微細なオフホワイト色の針状結晶として沈殿するようにし、これを真空濾過で単離した(14.6g、40.8mmol、43%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.53 (s, 2H), 2.48 (s, 6H), 1.34 (s, 24H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 140.7, 137.0, 83.5, 25.0, 21.6 ppm. HRMS (ESI) 計算値C20H33B2O4: m/z = 357.2632 ([M + H]+); 実測値m/z = 357.2614.
化合物(25)の合成:ジボロン酸エステル24(5.00g、13.9mmol、1.0当量)及び1,4-ジブロモ-2,5-ジメチルベンゼン(4)(18.4g、69.8mmol、5.0当量)を、脱気した2:1ジオキサン/H2O混合物(75mL)中に溶解した。CsF(12.7g、83.8mmol、6.0当量)及びPdCl2(dppf)(1.14g、1.40mmol、10mol%)を加え、これを16時間加熱還流した。反応混合物を室温に冷却してから、CH2Cl2及びH2Oで抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相を乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上に吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン)で処理することによって、無色の固体として化合物25を得た(2.18g、4.61mmol、33%収率)。1H NMR (500MHz, CD2Cl2, 25℃): δ = 7.47 (s, 2H), 7.04 (m, 2H), 6.95 (s, 2H), 2.39 (s, 6H), 2.05 (m, 6H), 2.02 (s, 6H) ppm. 13C NMR (126MHz, CD2Cl2, 25℃): δ = 141.2, 139.91, 139.89, 135.9, 135.1, 133.5, 133.2, 133.1, 132.1, 132.0, 130.9, 123.4, 22.5, 22.4, 19.4, 19.3, 19.2 ppm.
化合物(27)の合成:ボロン酸エステル9(600mg、1.04mmol、2.2当量)及びジブロミド26(265mg、0.473mmol、1.0当量)を、ジオキサン(10mL)及びH2O(5mL)の脱気した混合物中に溶解した。PdCl2(dppf)(38.4mg、0.047mmol、10mol%)及びCsF(431mg、2.84mmol、6.0当量)を加え、反応混合物を106℃に16時間加熱した。次いで、これを室温に冷却してから、CH2Cl2及びH2Oで抽出した。水相をCH2Cl2で2回洗浄した。合わせた有機相を乾燥させ(MgSO4)、濾過し、蒸発させた。粗生成物をシリカゲル上で吸収させ、カラムクロマトグラフィー(SiO2:ヘキサン:EtOAc=1:1)で処理することによって、無色の固体として化合物27を得た(485mg、0.373mmol、79%)。1H NMR (500MHz, CDCl3, 25℃): δ = 7.95 (d, J = 8.2Hz, 2H), 7.56 (d, J = 7.6Hz, 4H), 7.44 (t, J = 7.6Hz, 4H), 7.35 (t, J = 7.4Hz, 2H), 7.21 (s, 2H), 7.14 (s, 2H), 7.11 (s, 2H), 7.08-7.06 (m, 6H), 6.91 (s, 2H), 5.28 (s, 4H), 4.09 (m, 4H), 3.98 (s, 6H), 3.75 (m, 4H), 3.62 (m, 4H), 3.59 (s, 8H), 3.55 (m, 4H), 2.26 (d, 6H), 2.22 (s, 6H), 2.16 (2, 12H) ppm. 13C NMR (126MHz, CDCl3, 25℃): δ = 166.8, 157.9, 150.0, 147.6, 141.3, 140.0, 139.5, 137.4, 136.8, 134.0, 133.4, 132.5, 132.1, 131.68, 131.64, 130.86, 130.79, 130.5, 128.6, 127.8, 126.8, 121.7, 118.8, 116.1, 115.1, 71.9, 70.87, 70.79, 70.63, 70.55, 69.8, 69.2, 59.1, 52.1, 19.84, 19.72, 19.49, 19.44 ppm. HRMS (ESI) 計算値C82H91O14: m/z = 1299.6403 ([M + H]+); 実測値m/z = 1299.6454.
連結の合成手順。
連結IIIの合成:DMF(15mL)、THF(60mL)及び10重量%のPd/C(0.78g、0.73mmol)を、13(4.29g、7.32mmol)を充填したフラスコに加えた。反応フラスコをセプタムで密封し、不均質な溶液を、8インチステンレススチール針に取り付けられたバルーンにより送達されるH2でパージした。H2で膨張したバルーンを反応容器に取り付け、続いて予め50℃に温めた油浴に移した。反応混合物を24時間撹拌してから、室温に冷却し、N2流でパージし、濾過した。フィルターケーキをTHF(10mL)で洗浄し、合わせた濾液を真空中で濃縮することによって、生成物を得た。これを次のステップでそのまま使用した。
連結IVの合成:EtOAc(10mL)、EtOH(10mL)及び10重量%のPd/C(0.15g、0.15mmol)を、14(1.00g、1.45mmol)を充填したフラスコに加えた。反応フラスコをセプタムで密封し、不均質な溶液を、8インチステンレススチール針に取り付けられたバルーンにより送達されるH2でパージした。H2で膨張したバルーンを反応容器に取り付け、続いて予め50℃に温めた油浴に移した。反応混合物を24時間撹拌してから、室温に冷却し、N2流でパージし、濾過した。フィルターケーキをTHF(10mL)で洗浄し、合わせた濾液を真空中で濃縮することによって、生成物を得た。これを次のステップでそのまま使用した。
連結Vの合成:THF(20mL)及び10重量%のPd/C(0.29g、0.27mmol)を、15(2.16g、2.72mmol)を充填したフラスコに加えた。反応フラスコをセプタムで密封し、不均質な溶液を、8インチステンレススチール針に取り付けられたバルーンにより送達されるH2でパージした。H2で膨張したバルーンを反応容器に取り付け、続いてこの反応容器を予め50℃に温めた油浴に移した。反応混合物を24時間撹拌してから室温に冷却し、N2流でパージし、濾過した。フィルターケーキをTHF(10mL)で洗浄し、合わせた濾液を真空中で濃縮することによって、生成物を得た。これを次のステップでそのまま使用した。
連結V-hexの合成:出発物質18(455mg、0.467mmol、1.0当量)をTHF(10mL)中に溶解した。Pd/C(10%、50mg)を加えた。次いで反応混合物を、H2雰囲気下、50℃で一晩撹拌した。次いで、これを、セライトプラグを介して濾過し、THFで洗浄し、蒸発させ、真空で乾燥させた。
連結VIの合成:THF(60mL)を、16(2.0g、2.22mmol)を充填したフラスコに加えた。ラネーNi(およそ200mg、H2O中スラリーとして商業的に購入。このH2O中スラリーは、THFで逐次希釈し(5×)、続いて上清を除去することによってTHF中スラリーに変換した)を、ピペットを使用してフラスコに加えた。反応フラスコをセプタムで密封し、不均質な溶液を、8インチステンレススチール針に取り付けられたバルーンにより送達されるH2でパージした。H2で膨張したバルーンを反応容器に取り付け、続いてこの反応容器を予め50℃に温めた油浴に移した。反応混合物を48時間撹拌してから、室温に冷却し、N2流でパージした。これを、Erlenmeyerフラスコ(大部分のNiは磁気撹拌棒に結合したままである)にデカントしてから、CHCl3(100mL)で希釈した。次いで、溶液を還流にし、十分に充填したセライト床を介して高温濾過した。フィルターケーキをさらに高温のCHCl3ですすいだ。合わせた濾液を合わせ、真空中で濃縮することによって、生成物を得た。これを次のステップでそのまま使用した。
連結VIIの合成:出発物質19(1.19g、1.04mmol、1.0当量)をTHF(50mL)中に溶解した。Pd/C(10%、110mg)を加えた。次いで、反応混合物をH2雰囲気下、50℃で一晩撹拌した。次いで、これを、セライトプラグを介して濾過し、THFで洗浄し、蒸発させ、真空で乾燥させた。
連結VII-oegの合成:出発物質27(590mg、0.454mmol、1.0当量)をTHF(40mL)中に溶解した。ラネーNi(約10%mol)を加えた。次いで、反応混合物をH2雰囲気下、50℃で一晩撹拌した。次いで、これを、セライトプラグを介して濾過し、THFで洗浄し、蒸発させ、真空で乾燥させた。
連結IXの合成:出発物質20(827mg、0.612mmol、1.0当量)をTHF(50mL)中に溶解した。ラネーNi(約10%mol)を加えた。反応混合物を、H2雰囲気下、40℃で一晩撹拌した。次いで、これを、セライトプラグを介して濾過し、THFで洗浄し、蒸発させ、真空下で乾燥させた。
連結XIの合成:出発物質23(372mg、0.219mmol、1.0当量)をTHF(30mL)中に溶解した。ラネーNi(約10%mol)を加えた。反応混合物を、H2雰囲気下、40℃で一晩撹拌した。次いで、これを、セライトプラグを介して濾過し、THF、熱いCHCl3で洗浄し、蒸発させ、真空で乾燥させた。
IRMOF-74シリーズの合成。
概要:合成したIRMOF-74の試料は、この物質を平坦なアルミニウム試料ホルダーに取り付けられた粘着性の炭素表面上に分散させることによって測定した。次いで、電流15mAを維持しながら、アルゴン雰囲気内、周辺温度及び気圧70mTorrで30秒間、Hummer 6.2 Sputterを使用して、試料に金コーティングした。電圧を5から10kVに加速させて、SEI及びLEI検出器の両方を使用する、JEOL JSM-6701Fスキャニング電子顕微鏡を使用して試料を分析した。それぞれ合成したIRMOFの複数の試料を調査した。試料ホルダー上に堆積された一連の粒径の完全な検査後、独自の形態だけが明らかであった。他の相の存在に対する証拠は、調査した試料では観察されなかった。IRMOF-74シリーズの、異なるスケールのSEM画像が図17〜25に提示されている:IRMOF-74-IのSEM画像(図17);IMROF-74-IIのSEM画像(図18);IMROF-74-IIIのSEM画像(図19);IMROF-74-IVのSEM画像(図20);IMROF-74-VのSEM画像(図21);IMROF-74-VIのSEM画像(図22);IMROF-74-VIIのSEM画像(図23);IMROF-74-IXのSEM画像(図24);及びIMROF-74-XIのSEM画像(図25)。
IRMOF-74シリーズの活性化:IRMOF-74-I〜IVの合成されたままの試料を、DMFで3回洗浄してから、乾燥メタノール中に3日間浸した;この交換中に、乾燥メタノールを3回リフレッシュすることによって、水分子の配位を金属に完全に置き換えた。結果として生じるメタノール交換した試料を懸濁液としてクオーツセルに移し、溶媒をデカントした。次いで、IRMOF-74-I〜IVの試料を室温で10時間真空排気し(10-3Torr)、続いて130℃で12時間加熱することによって、メタノールを除去し、各金属上に空金属サイトを作り出した。配位メタノールの完全な除去を、活性化した試料の固体13C MAS NMRにおけるメタノールピークの不在により確認した。
すべての試料は、継続的な気流の雰囲気内で、白金パン内に保持された試料を用いて、TA Instruments Q-500シリーズ熱重量測定アナライザー上で作業した。すべてのTGA実験中、5℃分-1の一定速度で試料を加熱した。
4mm(外径)のジルコニアローターを有する標準的なBrukerマジック角回転(MAS)プローブを使用するBruker DSX-300分光器上で、高分解能な固体核磁気共鳴(NMR)スペクトルを周辺温度で記録した。MAS(CP/MAS)を用いた交差偏光を使用することによって、75.47MHzで13Cデータを取得した。1H及び13Cの90度パルス幅は両方とも4μsであった。CP接触時間は、1.5ms及び5msで変化させた。高いパワーの2パルス相モジュレーション(TPPM)1Hデカップリングをデータ収集中に適用した。デカップリング周波数は72kHzに対応した。MAS試料回転速度は10kHzであった。(CP/MAS)に対するスキャン間のリサイクル緩和は、化合物に応じて、3秒から20秒の間で変化したが、これは、1つのスキャンから次のスキャンで13Cの信号強度における明らかな損失が観測されなかったことにより判定された通りであった。13C化学シフトは、ゼロppmとしてのテトラメチルシランに対して与えられ、2次的参照として、37.77ppmに帰属されたアダマンタンのメチレン炭素信号を使用して較正される。
Ar吸着分析:50〜100mgの活性化したIRMOF-74を用いて、Autosorb-1自動式容量ガス吸着測定分析装置(Quantachrome、Boynton Beach、FL)上で、87KでAr等温線を記録した。得た等温線は、気体の吸着した量が気圧にプロットされているもので、この等温線から、BET及びLangmuirモデルに基づきIRMOF-74の特定の表面積を計算している。加えて、細孔サイズ分布及び細孔容積が取得可能である。複数の測定(3回以上)を、様々な重量を有する各IRMOFの異なるバッチに対して実施し、±5%の誤差で再現可能な結果を得た。極めて高純度等級のAr及びHe気体をすべての吸着測定において使用した。液体アルゴン槽(87K)を使用してAr(87K)等温線を測定した。IRMOF-74シリーズのAr等温線は、図47〜57に提示されている:IRMOF-74-I(図47);IRMOF-74-II(図48);IRMOF-74-III(図49);IRMOF-74-IV(図50);IRMOF-74-V(図51);IRMOF-74-V-hex(図52);IRMOF-74-VI(図53);IRMOF-74-VII(図54);IRMOF-74-VII-oeg(図55);IRMOF-74-IX(図56);及びIRMOF-74-XI(図57)。
一般的方法:ビタミン-B12及びミオグロビン(ウマの心臓由来、≧90%(SDS-Page)、本質的に塩を含まない、凍結乾燥された粉末)をSigma Aldrich Chemical Co.から購入した。金属有機多面体(MOP-18)を合成し、これまでに報告された手順により活性化した。メタノール(HPLC等級)をEMD Scienceから購入した。クロロホルム(HPLC等級、ペンタン安定化)をFisher Scientific International Inc.から購入した。緑色蛍光性タンパク質(GFP)(分子量:27 kDa.手順:(http:)www.uniprot.org/uniprot/P42212)及び0.1 Mリン酸塩緩衝剤溶液(PBS)(pH7.4)。1cmのHellmaクオーツ光学セルを使用して、Shimadzu UV1800で紫外可視分光光度(UV-Vis)の測定を実施した。誘導結合プラズマ発光分光(ICP-OES)の測定をThermo Jarrell Ash IRIS 1000ICP-OES上で行った。Mg、Co、Cu、及びFeのICP-OESのための基準となる1000ppm標準液を、Fisher Scientific International Inc.から購入した。共焦点顕微鏡画像化を、Leica TCS-SP1 Confocal Microscope上で実施した。
Claims (23)
- 一般的構造M-L-Mを含むMOF又はIRMOFであって、Mが金属を含み、Lが式I:
A1〜A8は、独立して、N又はCのいずれかであり、
X1及びX2はFGであり、
R1〜R12は、独立して、H、FG、(C1〜C12)アルキル、置換(C1〜C12)アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、(C1〜C12)シクロアルキル、置換(C1〜C12)シクロアルキル、アリール、置換アリール、ヘテロ環、置換ヘテロ環、-C(R13)3、-CH(R13)2、-CH2R13、-C(R13)3、-CH(R14)2、-CH2R14、-OC(R13)3、-OCH(R13)2、-OCH2R14、-OC(R14)3、-OCH(R14)2、-OCH2R14、
R13は、FG、(C1〜C12)アルキル、(C1〜C12)置換アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、ヘミアセタール、ヘミケタール、アセタール、ケタール、及びオルトエステルを含む群から選択され、
R14は、シクロアルキル、アリール、及びヘテロ環を含む群から選択される1つ以上の置換又は非置換の環であり、
yは、0〜3の数であり、
zは、0〜20の数であり、
ただし、NであるAと結合している場合、Rは不在であることを条件とする)
の連結部分である、MOF又はIRMOF。 - Mが遷移金属又はアルカリ土類金属のいずれかである、請求項1に記載のMOF又はIRMOF。
- MがMg又はZnのいずれかである、請求項1に記載のMOF又はIRMOF。
- X1及びX2がカルボン酸である、請求項3に記載のMOF又はIRMOF。
- A1〜A8がCである、請求項4に記載のMOF又はIRMOF。
- R1〜R10がヒドロキシルであり、
R2〜R5、R7、R9、R11及びR12が水素であり、
R6及びR8が、(C1〜C12)アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、及び置換ヘテロ-(C1〜C12)アルキニルからなる群から選択される、請求項5に記載のMOF又はIRMOF。 - R6及びR8が(C1〜C6)アルキルである、請求項6に記載のMOF又はIRMOF。
- zが1〜15の数である、請求項7に記載のMOF又はIRMOF。
- ポスト-フレームワーク反応物質をさらに含む、請求項1に記載のMOF又はIRMOF。
- ポスト-フレームワーク反応物質が、フレームワークの疎水性を低下させる、請求項9に記載のMOF又はIRMOF。
- 請求項1に記載のMOF又はIRMOFを作製する方法であって、溶媒、金属含有塩、及び式I:
A1〜A8は、独立して、N又はCのいずれかであり、
X1及びX2はFGであり、
R1〜R12は、独立して、H、FG、(C1〜C12)アルキル、置換(C1〜C12)アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、(C1〜C12)シクロアルキル、置換(C1〜C12)シクロアルキル、アリール、置換アリール、ヘテロ環、置換ヘテロ環、-C(R13)3、-CH(R13)2、-CH2R13、-C(R13)3、-CH(R14)2、-CH2R14、-OC(R13)3、-OCH(R13)2、-OCH2R14、-OC(R14)3、-OCH(R14)2、-OCH2R14、
R13は、FG、(C1〜C12)アルキル、(C1〜C12)置換アルキル、(C1〜C12)アルケニル、置換(C1〜C12)アルケニル、(C1〜C12)アルキニル、置換(C1〜C12)アルキニル、ヘテロ-(C1〜C12)アルキル、置換ヘテロ-(C1〜C12)アルキル、ヘテロ-(C1〜C12)アルケニル、置換ヘテロ-(C1〜C12)アルケニル、ヘテロ-(C1〜C12)アルキニル、置換ヘテロ-(C1〜C12)アルキニル、ヘミアセタール、ヘミケタール、アセタール、ケタール、及びオルトエステルを含む群から選択され、
R14は、シクロアルキル、アリール、及びヘテロ環を含む群から選択される1つ以上の置換又は非置換の環であり、
yは、0〜3の数であり、
zは、0〜20の数であり、
ただし、NであるAと結合している場合、Rは不在であることを条件とする)の連結部分を含む、高温での反応を含む、方法。 - 溶液、混合物、又は懸濁液からの1種以上の化学物質の吸着の方法であって、化学物質を、請求項1に記載のMOF又はIRMOFに接触させるステップを含む方法。
- 化学物質が有機分子である、請求項16に記載の方法。
- 化学物質が無機分子である、請求項16に記載の方法。
- MOF又はIRMOFがデバイス内に配置される、請求項17に記載の方法。
- デバイスがカラムである、請求項20に記載の方法。
- 1種以上の化学物質を多成分化学物質の溶液、混合物、又は懸濁液から分離するためのMOF又はIRMOF分離システムであって、入口及び出口と、入口及び出口の間のフローチャンバー内に配置された請求項1に記載のMOF又はIRMOFとを含むフローチャンバーを含むシステム。
- 請求項1に記載のMOF又はIRMOFと、薬学的活性のある薬剤とを含む、MOF又はIRMOFの薬剤送達デバイス。
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US20160008472A1 (en) | 2016-01-14 |
US9669098B2 (en) | 2017-06-06 |
KR20140081818A (ko) | 2014-07-01 |
JP6254086B2 (ja) | 2017-12-27 |
KR102011160B1 (ko) | 2019-08-14 |
US9078922B2 (en) | 2015-07-14 |
CN104302387A (zh) | 2015-01-21 |
WO2013112212A2 (en) | 2013-08-01 |
WO2013112212A3 (en) | 2014-10-09 |
US20130096210A1 (en) | 2013-04-18 |
CN104302387B (zh) | 2019-06-18 |
EP2766046B1 (en) | 2017-08-02 |
EP2766046A2 (en) | 2014-08-20 |
ES2645260T3 (es) | 2017-12-04 |
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