CN117801015A - 一种三价膦导向c-h活化制备膦炔杂化配体的方法 - Google Patents
一种三价膦导向c-h活化制备膦炔杂化配体的方法 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 33
- 238000010499 C–H functionalization reaction Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- -1 phosphine alkyne Chemical class 0.000 title claims abstract description 24
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000005922 Phosphane Substances 0.000 claims abstract description 15
- 229910000064 phosphane Inorganic materials 0.000 claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229940125904 compound 1 Drugs 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229940125782 compound 2 Drugs 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 125000002861 (C1-C4) alkanoyl group Chemical group 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229940126214 compound 3 Drugs 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000001041 indolyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000037 tert-butyldiphenylsilyl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1[Si]([H])([*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000010948 rhodium Substances 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052703 rhodium Inorganic materials 0.000 abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003504 photosensitizing agent Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000009396 hybridization Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 26
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
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- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910013594 LiOAc Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005885 boration reaction Methods 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 150000003003 phosphines Chemical class 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000011913 photoredox catalysis Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 239000002798 polar solvent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- SIOVKLKJSOKLIF-HJWRWDBZSA-N trimethylsilyl (1z)-n-trimethylsilylethanimidate Chemical compound C[Si](C)(C)OC(/C)=N\[Si](C)(C)C SIOVKLKJSOKLIF-HJWRWDBZSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5054—Preparation; Separation; Purification; Stabilisation by a process in which the phosphorus atom is not involved
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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Abstract
一种三价膦导向C‑H活化制备膦炔杂化配体的方法,利用可见光氧化还原催化与单一催化剂的P(III)定向C‑H活化相结合。在暴露于单一铑催化剂后,双芳基单膦底物可以用溴炔烃进行位点选择性C‑H活化,以理想的原子利用率、步骤和氧化还原经济方式进行对炔烃配体的模块化组装。其中,铑配合物通过利用光子能量进行C‑H活化和催化C‑C键的形成来发挥两种功能,制备得到的膦‑炔烃产物代表了一类新的配体,具有结合膦酸和π酸性质的杂化结构基序。该方法在不存在外源光敏剂的情况下,于室温及极为温和的反应条件中进行,具有优异的反应效果和官能团耐受性。
Description
技术领域
本发明属于有机合成领域,具体讲就是涉及一种三价膦导向C-H活化制备膦炔杂化配体的方法。
背景技术
在现有金属催化的C-H活化策略中,过渡金属(TM)积极参与C-H键的断裂,通过内部机制促进C-金属键的形成,定向基团被广泛用于螯合辅助的C-H活化,以控制位点选择性。现代光催化的出现极大地刺激了C-H功能化创新方法的发展,利用低能量光子的能量作为精确可控的能源,但这些方法大多涉及光敏的光氧化还原催化剂(PC),它通过氢原子转移或单电子转移促进转化。通过结合PC和过渡金属催化的双催化剂方法,可以引入具有有效选择性控制的独特官能团。
现有技术中,曾报道过单个过渡金属配合物既是光敏剂又是催化剂,在不需要外部光敏剂的情况下,可促进C–H键的功能化,在该方法中,2-芳基吡啶的C-H活化会导致环金属化配合物的形成,在可见光的激发下,该配合物会发生单电子转移,并在邻位或间位实现C-C偶联,但该技术方案在很大程度上依赖于与有机分子中的芳香族氮杂环的配位,这限制了其普遍适用性。
与氧和氮原子相比,在催化C-H活化中使用P(III)作为导向原子更具挑战性,因为它具有更强的金属配位和高离解能,这可能导致催化剂中毒。尽管如此,近年来,在P(III)引导的膦的C-H活化方面还是取得了进展,如:硼化、甲硅烷基化等。但为保持良好的活性和足够的周转次数,上述转化通常需在高温下进行。
由于现有技术中单个过渡金属配合物既是光敏剂又是催化剂的C-H活化方法存在对底物结构依赖性大,适用范围窄的缺点,而P(III)引导的膦的C-H活化为确保理想转化性,又存在需要在高温中进行的弊端,为了加快具有实际应用的手性配体的合成,迫切寻求一种适用性广,反应条件温和的C-H活化方法。
发明内容
本发明的技术目的就是针对现有金属催化的C-H活化策略中,对底物结构依赖性大,适用范围窄,以及需在高温中进行的缺点,提出的一种适用性广,反应条件温和的三价膦导向C-H活化制备膦炔杂化配体的方法。
技术方案
为了实现上述目的,本发明提供一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于,其合成路线如下:
其中:
Ar为芳香环或芳香杂环中的一种或多种;
R1为硅烷基;
R2为C1-C3烷基或C3-C6的环烷基或芳香基中的一种或多种;
R3和R4都为氢或C1-C3烷基或C1-C3烷氧基或卤素或C1-C3的卤代烷基或C1-C4的酯基或C1-C4的烷酰基中的一种或多种;
进一步地,R2为烷基或烷氧基或卤素或卤代烷基或C1-C4的酯基或C1-C4的烷酰基中的一种或多种。
进一步地,Ar为苯基或萘基或吡咯基或吡唑或呋喃基或吲哚基或吲唑中的一种或多种;
R1为三异丙基硅烷基或叔丁基二苯基硅烷基或叔丁基二甲基硅烷基的一种或多种;
R2为甲基或乙基或丙基或环丙基或环丁基或环戊基或环己基或苯环,以及被甲基或乙基或三氟甲基取代的甲基或乙基或丙基或环丙基或环丁基或环戊基或环己基或苯环中的一种或多种;
R3为甲基或乙基或氟或氯或溴或碘或三氟甲基或三氟甲氧基中的一种或多种。
进一步地,它包括以下步骤:
(1)将化合物1、化合物2、催化剂以及添加剂加入反应容器中,而后加入有机溶剂I,将所得反应混合物在可见光照射下,室温下搅拌(10-60)h;
(2)反应完成后,将反应物减压蒸,所得浓缩物经纯化,得到目标化合物3。
进一步地,步骤(1)中,反应在惰性气体保护下进行。
进一步地,惰性气体为氮气或氩气中的一种或多种;
进一步地,步骤(1)中,所述有机溶剂I为乙腈或二甲基亚砜或二氧六环或四氢呋喃或N,N-二甲基甲酰胺或二氯甲烷或二氯乙烷或氯仿或甲苯或二甲苯中的一种或多种。
进一步地,所述有机溶剂I为二氯甲烷或甲苯或四氢呋喃。
进一步地,步骤(1)中,所述催化剂为铑催化剂。
进一步地,所述铑催化剂为[Rh(cod)Cl]2、Rh2(OAc)4中的一种或多种。
进一步地,步骤(1)中,所述添加剂为Na2CO3或NaOAc或Na2HPO4或Na2HPO4·12H2O以及Na2HPO4与水组合中的一种或多种。
进一步地,所述添加剂优选为Na2HPO4·12H2O或Na2HPO4与水组合中的一种或多种;
进一步地,步骤(1)中,可见光为蓝光。
进一步地,所述可见光优选为LED蓝光光源。
进一步地,步骤(1)中,化合物1、化合物2、催化剂、添加剂的摩尔比为1:(1~3.0):(0.003~0.1):(1.5~4)。
进一步地,化合物1、化合物2、催化剂、添加剂的摩尔比优选为1:1.8:(0.005~0.01):2或1:3.0:(0.005~0.01):4。
进一步地,步骤(1)中,化合物1与有机溶剂I的质量体积比为1g/5~50mL;
进一步地,步骤(1)中,反应时长优先30~50h。
进一步地,步骤(1)中,纯化方式为柱层析或重结晶或蒸馏中的一种或多种。
有益效果
本发明提供的一种三价膦导向C-H活化制备膦炔杂化配体的方法,利用可见光光氧化还原催化与使用单一催化剂的P(III)定向C-H活化相结合。在暴露于单一铑催化剂后,双芳基单膦可以用溴炔烃进行位点选择性C-H活化,以理想的原子、步骤和氧化还原经济方式进行对炔烃配体的模块化组装。其中,铑配合物通过利用光子能量进行C-H活化和催化C-C键的形成来发挥两种功能,获得的膦-炔烃产物代表了一类新的配体,其很难用已知方法制备。所述合成方法在开发用于催化和有机金属反应的高效杂化配体系统方面构建了一个新入口。
附图说明
附图1是本发明实施例1中化合物3aa的核磁氢谱图;
附图2是本发明实施例1中化合物3aa的核磁碳谱图;
附图3是本发明实施例1中化合物3aa的核磁磷谱图;
附图4是本发明实施例11中化合物3ab的核磁氢谱图;
附图5是本发明实施例11中化合物3ab的核磁碳谱图;
附图6是本发明实施例11中化合物3ab的核磁磷谱图;
附图7是本发明实施例12中化合物3ac的核磁氢谱图;
附图8是本发明实施例12中化合物3ac的核磁碳谱图;
附图9是本发明实施例12中化合物3ac的核磁磷谱图;
附图10是本发明实施例12中化合物3ac的核磁氟谱图;
附图11是本发明实施例13化合物3ad的核磁氢谱图;
附图12是本发明实施例13化合物3ad的核磁碳谱图;
附图13是本发明实施例13化合物3ad的核磁磷谱图。
具体实施方式
为使本发明实施例的技术方案和优点更加清楚,下面将结合本发明实施例的附图,对本发明实施例的技术方案进行清楚、完整地描述。显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例。基于所描述的本发明的实施例,本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。除非另作定义,此处使用的技术术语或者科学术语应当为本发明所属领域内具有一般技能的人士所理解的通常意义。
本实施例提供的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其合成路线如下:
其中:
Ar为芳香环或芳香杂环中的一种或多种;
R1为硅烷基;
R2为C1-C3烷基或C3-C6的环烷基或芳香基中的一种或多种;
R3和R4都为氢或C1-C3烷基或C1-C3烷氧基或卤素或C1-C3的卤代烷基或C1-C4的酯基或C1-C4的烷酰基中的一种或多种;
下面通过实施例等对发明进行进一步说明。
以下实施例中除非特别说明,所用试剂和材料均为市购。
实施例1
如附图1,2和3所示的化合物(2'-((1-((叔丁基二甲基甲硅烷基)氧基)环己基)乙炔基)-6'-((三异丙基甲硅烷基(乙炔基))-[1,1'-联苯]-2-基)二苯基膦(3aa)的合成
向25mL Schlenk管中加入化合物1a(67.6mg,0.20mmol)、化合物2a(94.1mg,0.36mmol),[Rh(cod)Cl]2(4.9mg,0.01mmol)和Na2HPO4.12H2O(143.3mg,0.40mmol),用Ar吹扫管三次,而后加入无水DCM(1.0mL)。将所得混合物在Ar气氛中,蓝色LED照射下,室温反应48h。反应完成后,在减压蒸馏除去溶剂,粗产物在硅胶上通过柱色谱法(石油醚/甲苯=10/1)纯化,得到无色油状化合物3aa 73.6mg,收率71%。
1H NMR(500MHz,CDCl3)δ7.56(d,J=7.7Hz,1H),7.41–7.32(m,5H),7.28–7.20(m,9H),7.11(td,J=7.6,1.2Hz,1H),7.06(dd,J=7.6,4.0Hz,1H),6.96(d,J=7.7Hz,1H),0.99(s,21H).
13C NMR(126MHz,CDCl3)δ146.6(d,J=29.6Hz),144.1(d,J=6.5Hz),136.2(d,J=11.3Hz),134.2(d,J=20.0Hz),133.7,133.7(d,J=18.9Hz),132.8,130.5(d,J=5.0Hz),130.4(d,J=5.1Hz),128.6,128.3,128.1,127.6,127.1,127.0,123.1,106.1,94.1,18.6,11.2.
31P NMR(202MHz,CDCl3)δ-13.46.
ATR-FTIR(cm-1):3010,2166,1523,1277,755.
HRMS-ESI:m/z calculated for C35H40PSi+[M+H+]519.2631,found 519.2620.
为进一步探究不同反应条件对反应结果的影响,实施例2-10及对比例1-6修改了单一反应变量,测试各反应条件对反应结果的影响,所得结果列于表1中。
表1
a.产物分离收率;b.将反应至于空气中;c.将反应至于黑暗中。
由上表可知,实施例2-5及对比例1相较实施例1而言,改变了添加剂的种类,反应结果表明,Na2HPO4·12H2O对反应的促进作用最为优异,其次使用不含水的Na2HPO4反应较含结晶水的Na2HPO4·12H2O,反应收率有所降低,当使用Na2HPO4与水的组合作为添加剂时,反应收率有所改善,可见水在反应中的重要作用。实施例6及对比例2-4相较于实施例1而言,改变了催化剂的种类,反应结果表明,除[Rh(cod)Cl]2外,Rh(II)的催化剂,如Rh2(OAc)4对反应也起到了一定的促进作用,而Rh(III)催化剂的应用,如[RhCp*Cl2]2,则未能得到目标化合物,表明其对反应无促进作用,其他过渡金属催化剂,如铱([Ir(cod)Cl]2)、钌([RuCl2(p-cymene)]2)等,同样对反应也未起到促进作用。实施例7则将催化剂的负载量降低了一半,降低了反应速率,反应收率有所降低。实施例8-9相较于实施例1而言,调整了反应溶剂,其中,非极性溶剂甲苯对反应的促进作用略逊于二氯甲烷,而极性溶剂N,N-二甲基甲酰胺则对反应的促进作用进一步降低。实施例10中进行了敞口反应,反应收率降低明显,可见惰性气体保护,对该反应也起到较为积极的作用。对比例5将反应至于黑暗中,升温至80℃反应,反应收率减低明显,对比例6同样将反应至于黑暗中,室温反应,则未能检测到产物,佐证了该反应中,光照对反应的重要作用。
实施例11
如附图4,5和6所示的化合物(5'-甲氧基-2'-(三异丙基甲硅烷基)乙炔基)-[1,1'-联苯]-2-基)二苯基膦(3ab)的合成
参照实施例1,使用1b(73.7mg,0.20mmol),2a(94.1mg,0.36mmol),[Rh(COD)Cl]2(4.9mg,0.01mmol)以及Na2HPO4.12H2O(143.3mg,0.40mmol)参与反应,得到82.6mg无色油状物3ab,收率75%。
1H NMR(500MHz,CDCl3)δ7.39(d,J=8.5Hz,1H),7.27–7.21(m,6H),7.17–7.09(m,7H),6.93(dd,J=7.4,3.7Hz,1H),6.69–6.67(m,1H),6.26(d,J=2.0Hz,1H),3.21(s,3H),0.87(s,21H).
13C NMR(126MHz,CDCl3)δ158.3,146.8(d,J=30.2Hz),145.9(d,J=6.9Hz),137.8(d,J=12.0Hz),136.1(d,J=12.4Hz),134.3(d,J=20.1Hz),134.1,133.9,133.9(d,J=20.1Hz),130.5(d,J=5.1Hz),128.7,128.6(d,J=7.1Hz),128.5,128.3,128.2,127.8,115.4,114.9(d,J=4.8Hz),114.8,106.2,92.2,54.9,18.8,11.4.31P NMR(202MHz,CDCl3)δ-13.67.
ATR-FTIR(cm-1):2941,2890,2862,1601,1464,1219,1033,882,740.
HRMS-ESI:m/z calculated for C36H42OPSi+[M+H+]549.2737,found 549.2734.实施例12
如附图7,8,9和10所示的化合物二苯基(5-(三氟甲基)-2'-((三异丙基甲硅烷基)乙炔基)-[1,1'-联苯]-2-基)膦(3ac)的合成
参照实施例1,使用1c(91.2mg,0.20mmol),2a(94.1mg,0.36mmol),[Rh(COD)Cl]2(4.9mg,0.01mmol)以及Na2HPO4.12H2O(143.3mg,0.40mmol)参与反应,得到95.2mg无色油状物3ac,收率81%。
1H NMR(500MHz,CDCl3)δ7.60–7.57(m,1H),7.54(d,J=7.7Hz,1H),7.48(d,J=9.5Hz,1H),7.35(dt,J=14.4,7.2Hz,3H),7.30–7.26(m,2H),7.25–7.22(m,4H),7.21–7.17(m,2H),7.14(dd,J=8.1,3.3Hz,1H),7.07(t,J=7.6Hz,1H),6.84(d,J=7.7Hz,1H),0.95(d,J=3.4Hz,21H).
13C NMR(126MHz,CDCl3)δ147.0(d,J=29.4Hz),142.5(d,J=6.2Hz),142.1(d,J=16.5Hz),136.3(d,J=11.6Hz),136.1(d,J=10.9Hz),134.3(d,J=20.7Hz),133.83,133.80(d,J=20.2Hz),132.9,130.2(d,J=4.7Hz),129.0,128.7,128.6(d,J=7.5Hz),128.4(d,J=6.9Hz),128.3(d,J=7.0Hz),127.7,127.2,126.9(q,J=4.0Hz),124.2(q,J=3.8Hz),124.1(q,J=273.4Hz),123.1,105.5,94.9,18.5,11.1.
31P NMR(202MHz,CDCl3)δ-13.27.
19F NMR(471MHz,CDCl3)δ-62.59.
ATR-FTIR(cm-1):2942,2891,2864,1463,1332,1169,1092,1018,742.
HRMS-ESI:m/z calculated for C36H38F3NaPSi+[M+Na+]609.2325,found609.2319.
实施例13
如附图11,12和13所示的化合物二苯基(2'-((三异丙基甲硅烷基)乙炔基)-[1,1'-联萘]-2-基)膦(3ad)的合成
参照实施例1,采用1d(878mg,2mmol),2a(1.56g,6mmol,3.0equiv.),[Rh(COD)Cl]2(69.2mg,0.14mmol,0.07equiv.)以及Na2HPO4.12H2O(2.9g,8.0mmol,4.0equiv.)在THF(10mL)中,反应72h,得到亮黄色油状物691.8mg3ad,收率56%,>99%ee。
1H NMR(400MHz,CDCl3)δ7.92(d,J=8.48Hz,1H),7.89–7.81(m,3H),7.76(d,J=8.46Hz,1H),7.49–7.42(m,2H),7.37–7.27(m,5H),7.24–7.03(m,8H),6.86(q,J=8.52Hz,2H),0.75(d,J=3.77Hz,21H).
13C NMR(101MHz,CDCl3)δ144.7(d,J=35.4Hz),141.4(d,J=8.7Hz),138.7(d,J=12.7Hz),137.0(d,J=12.8Hz),135.4(d,J=11.3Hz),134.2(d,J=20.Hz),134.0,133.2(d,J=19.0Hz),132.9(d,J=7.5Hz),132.7,130.5(d,J=1.8Hz),129.2,128.5,128.22,128.17,128.1(d,J=3.0Hz),127.92127.89,127.83,127.2,127.0(d,J=3.0Hz),126.8,126.5,126.3,126.1,122.2(d,J=2.3Hz),106.6,95.2,18.5(d,J=6.3Hz),11.1.
31PNMR(162MHz,CDCl3)δ-14.87.
ATR-FTIR(cm-1):3052,2940,2862,2144,1585,1462,1433,1266,882,741.
HRMS-ESI:m/z calculated for C43H44PSi+[M+H+]619.2944,found 619.2943.应用例
为确认所得膦炔杂化配体的实用性,将所得化合物3ad作为配体,用于钯催化的丙二酸二乙酯(化合物6)与乙酸烯丙酯(化合物7)的Tsuji Trost烷基化反应中。
在室温和氩气气氛下,向手性配体3ad(9.9mg,0.016mmol)、[Pd(η3-C3H5)Cl]2(2.9mg,0.008mmol)和LiOAc(1.1mg,0.016mm mol)在乙醚(1mL)中的混合物中,加入N,O-双(三甲基甲硅烷基)乙酰胺(BSA,122.1mg,0.6mmol)和乙酸烯丙酯(50.4mg,0.2mmol)。30分钟后,加入丙二酸二乙酯(96.0mg,0.6mmol)。在-5℃下反应14小时,反应完成后,用乙醚和水稀释反应混合物,有机层用盐水洗涤,并用Na2SO4干燥,过滤,将滤液浓缩并通过柱色谱法(石油醚:乙酸乙酯=5:1)纯化,得到化合物8(51.2mg,73%产率,90%ee)。
1H NMR(500MHz,CDCl3)δ7.29–7.08(m,10H),6.40(dd,J=15.7,2.4Hz,1H),6.26(ddd,J=15.7,8.6,2.5Hz,1H),4.19(ddd,J=11.2,8.6,2.8Hz,1H),4.15–4.05(m,2H),3.96–3.80(m,3H),1.12(t,J=7.1Hz,3H),0.92(t,J=7.1Hz,3H).13C NMR(126MHz,CDCl3)δ168.0,167.5,140.4,137.0,131.8,129.5,128.8,128.6,128.1,127.6,127.2,126.5,61.7,61.5,57.9,49.3,14.2,13.9.
同时,为了比较化合物3ad作为配体的反应活性,还选择了配体4及配体5进行对比实验。
反应结果显示,配体4参与反应时,收率仅为24%,目标产物ee值小于5%,而配体5参与反应时,则得到了相反构型的化合物,故而,二者对反应的促进作用均远低于化合物3ad。
Claims (10)
1.一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于,其合成路线如下:
其中:
Ar为芳香环或芳香杂环中的一种或多种;
R1为硅烷基;
R2为C1-C3烷基或C3-C6的环烷基或芳香基中的一种或多种;
R3和R4都为氢或C1-C3烷基或C1-C3烷氧基或卤素或C1-C3的卤代烷基或C1-C4的酯基或C1-C4的烷酰基中的一种或多种。
2.如权利要求1所述的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于:Ar为苯基或萘基或吡咯基或吡唑或呋喃基或吲哚基或吲唑中的一种或多种;
R1为三异丙基硅烷基或叔丁基二苯基硅烷基或叔丁基二甲基硅烷基的一种或多种;
R2为甲基或乙基或丙基或环丙基或环丁基或环戊基或环己基或苯环,以及被甲基或乙基或三氟甲基相应取代的甲基或乙基或丙基或环丙基或环丁基或环戊基或环己基或苯环中的一种或多种;
R3为甲基或乙基或氟或氯或溴或碘或三氟甲基或三氟甲氧基中的一种或多种。
3.如权利要求1所述的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于,它包括以下步骤:
(1)将化合物1、化合物2、催化剂以及添加剂加入反应容器中,而后加入有机溶剂I,将所得反应混合物在可见光照射下,室温下搅拌(10-60)h;
(2)反应完成后,将反应物减压蒸,所得浓缩物经纯化,得到目标化合物3。
4.如权利要求3所述的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于:步骤(1)中,反应用惰性气体进行保护。
5.如权利要求3所述的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于:步骤(1)中,所述有机溶剂I为乙腈或二甲基亚砜或二氧六环或四氢呋喃或N,N-二甲基甲酰胺或二氯甲烷或二氯乙烷或氯仿或甲苯或二甲苯中的一种或多种。
6.如权利要求3所述的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于:步骤(1)中,所述催化剂为[Rh(cod)Cl]2或Rh2(OAc)4中的一种或多种。
7.如权利要求3所述的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于:步骤(1)中,所述添加剂为Na2CO3或NaOAc或Na2HPO4或Na2HPO4·12H2O或Na2HPO4与水的组合物中的一种或多种。
8.如权利要求4所述的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于:步骤(1)中,可见光为蓝光。
9.如权利要求4所述的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于:步骤(1)中,化合物1、化合物2、催化剂、添加剂的摩尔比为1:(1~3.0):(0.003~0.1):(1.5~4)。
10.如权利要求4所述的一种三价膦导向C-H活化制备膦炔杂化配体的方法,其特征在于:步骤(1)中,化合物1与有机溶剂I的质量体积比为1g/5~50mL,反应时长优先30~50h。
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