CN114933511A - 一种羧基快速转化为醛基的方法 - Google Patents
一种羧基快速转化为醛基的方法 Download PDFInfo
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- CN114933511A CN114933511A CN202210685291.7A CN202210685291A CN114933511A CN 114933511 A CN114933511 A CN 114933511A CN 202210685291 A CN202210685291 A CN 202210685291A CN 114933511 A CN114933511 A CN 114933511A
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- Prior art keywords
- nmr
- cdcl
- pyridine
- dichloromethane
- compound
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 13
- 125000003172 aldehyde group Chemical group 0.000 title claims abstract description 8
- -1 aldehyde compound Chemical class 0.000 claims abstract description 102
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 239000002904 solvent Substances 0.000 claims abstract description 29
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 24
- NLPOZSHCOAICQC-UHFFFAOYSA-N 2-(trifluoromethylsulfonyl)pyridine Chemical class FC(F)(F)S(=O)(=O)C1=CC=CC=N1 NLPOZSHCOAICQC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000085 borane Inorganic materials 0.000 claims abstract description 16
- 150000007530 organic bases Chemical class 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 414
- 238000000605 extraction Methods 0.000 claims description 68
- 238000000926 separation method Methods 0.000 claims description 66
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- FFFLZWJKFLYZPS-UHFFFAOYSA-N n,n-diphenylpyridin-4-amine Chemical compound C1=CC=CC=C1N(C=1C=CN=CC=1)C1=CC=CC=C1 FFFLZWJKFLYZPS-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000003849 aromatic solvent Substances 0.000 claims 1
- 239000004210 ether based solvent Substances 0.000 claims 1
- 239000005453 ketone based solvent Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 137
- 238000004440 column chromatography Methods 0.000 description 69
- VWAJWTVHJDPSOQ-UHFFFAOYSA-N 1-(trifluoromethylsulfonyl)pyridin-1-ium Chemical class FC(F)(F)S(=O)(=O)[N+]1=CC=CC=C1 VWAJWTVHJDPSOQ-UHFFFAOYSA-N 0.000 description 68
- 239000007864 aqueous solution Substances 0.000 description 68
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 description 60
- 239000012299 nitrogen atmosphere Substances 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 238000003756 stirring Methods 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 239000011734 sodium Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 150000001299 aldehydes Chemical class 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- CQQSQBRPAJSTFB-UHFFFAOYSA-N 4-(bromomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CBr)C=C1 CQQSQBRPAJSTFB-UHFFFAOYSA-N 0.000 description 2
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- KPSRODZRAIWAKH-JTQLQIEISA-N Ciprofibrate Natural products C1=CC(OC(C)(C)C(O)=O)=CC=C1[C@H]1C(Cl)(Cl)C1 KPSRODZRAIWAKH-JTQLQIEISA-N 0.000 description 2
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- HCUARRIEZVDMPT-UHFFFAOYSA-N Indole-2-carboxylic acid Chemical compound C1=CC=C2NC(C(=O)O)=CC2=C1 HCUARRIEZVDMPT-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
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- 238000012423 maintenance Methods 0.000 description 1
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- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
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Abstract
本发明公开了一种羧基快速转化为醛基的方法。所述方法包括:使包含羧酸类化合物、有机碱、三氟甲磺酰基吡啶盐、硼烷类化合物和溶剂的混合反应体系进行反应,制得醛类化合物。本发明提供的方法反应操作简单,可以在空气与少量水分的环境下进行,反应条件温和、高效,具有良好的官能团兼容性;所制得的醛类化合物在生物、医药、材料等领域有着重要的作用。
Description
技术领域
本发明属于精细化工技术领域,涉及一种羧基快速转化为醛基的方法,尤其涉及一种通过新型三氟甲磺酰基吡啶盐试剂类化合物将羧酸快速活化,然后与硼烷反应合成醛类化合物的方法。
背景技术
羧酸在自然界中易于获得、稳定且丰富,在合成化学中是一种常用的原料。另外,因为其衍生物在药物、农用化学品、功能材料和进一步的合成转化中发挥着重要的作用,所以开发羧酸高效转化的方法是有机化学中最重要的研究之一。醛作为羧酸的一种重要转化产物,其常用的合成方法有以下两种:1)先使用强还原剂将羧酸还原成醇,然后再将醇氧化成醛;2)先将羧酸转化为活性较高的羧酸衍生物,然后经过选择性还原方法得到醛类化合物。在醇的氧化过程中,需要化学计量量的氧化剂,并且会产生形成难处理的副产物。虽然羧酸衍生物的还原成醛是一种常用的方法,但该反应一般需要化学计量的金属氢化物,并且需要在低温下进行以避免其他官能团的还原。因此,发展一种高效、简单、构型保持地羧酸转化为醛的方法具有重要的实际应用价值。
发明内容
本发明的主要目的在于提供一种羧基快速转化为醛基的方法,以克服现有技术的不足。
为实现前述发明目的,本发明采用的技术方案包括:
本发明实施例提供了一种羧基快速转化为醛基的方法,其包括:使包含羧酸类化合物、有机碱、三氟甲磺酰基吡啶盐、硼烷类化合物和溶剂的混合反应体系进行反应,制得醛类化合物。
在一些较为具体的实施方案中,所述三氟甲磺酰基吡啶盐具有如式(II)-(VII)中任一者所示的结构:
其中,R1选自甲氧基、氰基、硝基、卤素中的任一者;Tf为SO2CF3。
与现有技术相比,本发明的有益效果在于:
(1)本发明提供的一种通过新型三氟甲磺酰基吡啶盐试剂将羧基快速活化,并与硼烷反应制备醛的方法,反应操作简单、无惧空气与少量水分,反应条件温和、高效,具有良好的官能团兼容性;所得的醛类化合物在生物、医药、材料等领域有着重要的作用;
(2)本发明提供的一种通过新型三氟甲磺酰基吡啶盐试剂将羧基快速活化,并与硼烷反应制备醛的方法,当使用手性羧酸作为反应物,其产物几乎不会发生外消旋化(ee值最高为大于99%);另外反应体系为均相体系,可以使用流动化学的方法实现羧酸化合物的转化。
具体实施方式
鉴于现有技术的缺陷,本案发明人经长期研究和大量实践,得以提出本发明的技术方案,下面将对本发明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一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动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。
具体的,作为本发明技术方案的一个方面,其所涉及的一种羧基快速转化为醛基的方法包括:使包含羧酸类化合物、有机碱、三氟甲磺酰基吡啶盐(Tf-PyridiniumReagent)、硼烷类化合物和溶剂的混合反应体系进行反应,制得醛类化合物。
在一些较为具体的实施方案中,所述羧基快速转化为醛基方法的反应方程式如下式所示:
在一些优选实施方案中,所述羧酸类化合物具有如式(I)所示的结构:
其中,R选自碳原子数为1~43的烷基、烯基、炔基、芳基中的任意一种。
在一些优选实施方案中,所述三氟甲磺酰基吡啶盐具有如式(II)-(VII)中任一者所示的结构:
其中,R1选自甲氧基、氰基、硝基、卤素(-F、-Cl、-Br)中的任一者;Tf为SO2CF3。
在一些优选实施方案中,所述硼烷类化合物包括硼烷和/或者氘代硼烷,且不限于此。
在一些优选实施方案中,所述硼烷类化合物具有如式(VIII)-(XI)所示的结构:
其中,R1和R2为选自碳原子数为1~10的烷基或芳基,L为吡啶、三乙胺、卡宾等具有配位性的基团。
进一步地,所述三氟甲磺酰基吡啶盐具有如式(III)所示的结构:
进一步地,所述硼烷具有如式(VIII)所示的结构:
在一些优选实施方案中,所述有机碱包括吡啶类化合物、三乙胺、N-甲基吗啉、N,N-二异丙基乙胺、1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,4-二氮杂二环[2.2.2]辛烷、2,2,6,6-四甲基哌啶中的任意一种或两种以上的组合,且不限于此。
进一步地,所述吡啶类化合物包括吡啶、4-二甲氨基吡啶、1-吡啶-4-哌啶、4-吡咯烷基吡啶、4-吗啉吡啶、N,N-二苯基吡啶-4-胺中的任意一种或两种以上的组合,且不限于此。
在一些优选实施方案中,所述羧酸类化合物、有机碱、三氟甲磺酰基吡啶盐与硼烷类化合物的摩尔比为1.0∶(1.0~2.2)∶(1.0~2.2)∶(1.0~2.0)。
在一些优选实施方案中,所述方法包括:在保护性气氛或者干燥空气气氛中,于0~25℃将羧酸类化合物、有机碱与溶剂混合,获得第一混合物。
在一些优选实施方案中,所述方法包括:于0~25℃依次向所述第一混合物加入三氟甲磺酰基吡啶盐、硼烷类化合物形成所述混合反应体系并反应5~60min,制得所述醛类化合物。
在一些优选实施方案中,所述方法包括:于0~25℃依次向所述第一混合物加入硼烷类化合物、三氟甲磺酰基吡啶盐形成所述混合反应体系并反应5~60min,制得所述醛类化合物。
在一些优选实施方案中,所述方法还包括:在所述反应完成后,对所获混合物进行萃取、干燥、分离处理。
在一些更为具体的实施方案中,所述方法还包括:在所述反应完成后,向所获混合物中加入萃取剂进行萃取,取有机层用干燥剂进行干燥,再采用柱层析进行分离,获得所述醛类化合物。
进一步的,所述萃取剂包括碳酸氢钠水溶液以及乙酸乙酯,且不限于此。
进一步的,所述干燥剂包括无水硫酸钠,且不限于此。
在一些优选实施方案中,所述溶剂包括卤代烷烃类溶剂、醚类溶剂、腈类溶剂、芳烃类溶剂、酮类溶剂、酰胺类溶剂中的任意一种或两种以上的组合,且不限于此。
进一步地,所述卤代烷烃类溶剂包括二氯甲烷和/或1,2-二氯乙烷,且不限于此。
进一步地,所述腈类溶剂包括乙腈,且不限于此。
进一步地,所述芳烃类溶剂包括甲苯,且不限于此。
进一步地,所述醚类溶剂包括四氢呋喃,且不限于此。
进一步地,所述酮类溶剂包括丙酮,且不限于此。
进一步地,所述酰胺类溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中的任意一种或两种以上的组合,且不限于此。
本发明实施例的另一个方面还提供了前述制备的醛类化合物于生物、医药、材料领域中的用途。
下面结合若干优选实施例对本发明的技术方案做进一步详细说明,本实施例在以发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
下面所用的实施例中所采用的实验材料,如无特殊说明,均可由常规的生化试剂公司购买得到。
实施例1
氮气氛围下,在一个25mL Schlenk管中加入4-甲硫基苯甲酸(1.0mmol,168.0mg),1-吡啶-4-哌啶(PPDP,1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为83%。
1H NMR(400MHz,CDCl3)δ9.91(s,1H),7.76(d,J=8.0Hz,2H),7.31(d,J=8.0Hz,2H),2.53(s,3H)ppm;13C NMR(101MHz,CDCl3)δ191.2,147.8,132.8,129.9,125.1,14.5ppm.
实施例2
氮气氛围下,在一个25mL Schlenk管中加入4-甲氧基苯甲酸(1.0mmol,152.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为71%。
1H NMR(400MHz,CDCl3)δ9.88(s,1H),7.84(d,J=8.8Hz,2H),7.00(d,J=8.8Hz,2H),3.89(s,3H)ppm;13C NMR(101MHz,CDCl3)δ190.8,164.6,131.9,129.9,114.3,55.5ppm.
实施例3
氮气氛围下,在一个25mL Schlenk管中加入4-苯基苯甲酸(1.0mmol,198.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为82%。
1H NMR(400MHz,CDCl3)δ10.04(s,1H),7.93(d,J=6.8Hz,2H),7.73(d,J=7.6Hz,2H),7.62(d,J=7.6Hz,2H),7.51-7.38(m,3H)ppm;13C NMR(101MHz,CDCl3)δ191.9,147.1,139.6,135.1,130.2,128.9,128.4,127.6,127.3.ppm.
实施例4
氮气氛围下,在一个25mL Schlenk管中加入二苯并噻吩-3-羧酸-13C(1.0mmol,229.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入HBpin(1.5mmol,192.0mg)和三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为81%。
1H NMR(400MHz,CDCl3)δ9.98(s,1H),7.91(d,J=8.4Hz,2H),7.27(d,J=8.4Hz,2H),2.33(s,3H)ppm;13C NMR(101MHz,CDCl3)δ190.8,168.6,155.3,133.9,131.1,122.3,21.0ppm.
实施例5
氮气氛围下,在一个25mL Schlenk管中加入4-氯苯甲酸(1.0mmol,156.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为69%。
1H NMR(400MHz,CDCl3)δ9.99(s,1H),7.83(d,J=8.0Hz,2H),7.52(d,J=8.0Hz,2H)ppm;13C NMR(101MHz,CDCl3)δ190.8,140.9,134.7,130.9,129.4ppm.
实施例6
氮气氛围下,在一个25mL Schlenk管中加入4-溴苯甲酸(1.0mmol,199.9mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为82%。
1H NMR(400MHz,CDCl3)δ9.98(s,1H),7.75(d,J=8.0Hz,2H),7.69(d,J=8.0Hz,2H)ppm;13C NMR(101MHz,CDCl3)δ191.1,135.0,132.4,130.9,129.8ppm.
实施例7
氮气氛围下,在一个25mL Schlenk管中加入4-碘苯甲酸(1.0mmol,247.9mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为82%。
1H NMR(400MHz,CDCl3)δ9.96(s,1H),7.92(d,J=8.4Hz,2H),7.59(d,J=8.4Hz,2H)ppm;13C NMR(101 MHz,CDCl3)δ191.4,138.4,135.6,130.8,102.8ppm.
实施例8
氮气氛围下,在一个25mL Schlenk管中加入4-硝基苯甲酸(1.0mmol,167.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为61%。
1H NMR(400MHz,CDCl3)δ10.17(s,1H),8.40(d,J=8.4Hz,2H),8.09(d,J=8.4Hz,2H)ppm;13C NMR(101MHz,CDCl3)δ190.2,151.2,140.1,130.5,124.3ppm.
实施例9
氮气氛围下,在一个25mL Schlenk管中加入4-硝基苯甲酸(1.0mmol,147.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为78%。
1H NMR(400MHz,CDCl3)δ10.11(s,1H),8.01(d,J=7.6Hz,2H),7.86(d,J=7.6Hz,2H)ppm;13C NMR(101MHz,CDCl3)δ190.6,138.7,132.9,129.9,117.7,117.5ppm.
实施例10
氮气氛围下,在一个25mL Schlenk管中加入4-硝基苯甲酸(1.0mmol,147.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为64%。
1H NMR(400MHz,CDCl3)δ10.07(s,1H),8.18(s,1H),8.14(d,J=7.6Hz,1H),7.93(d,J=7.6Hz,1H),7.72(t,J=7.6Hz,1H)ppm;13C NMR(101MHz,CDCl3)δ189.9,137.1,136.8,133.2,133.1,130.1,117.5,113.6ppm.
实施例11
氮气氛围下,在一个25mL Schlenk管中加入4-乙酰基苯甲酸(1.0mmol,164.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为77%。
1H NMR(400MHz,CDCl3)δ10.11(s,1H),8.11(d,J=8.0Hz,2H),7.99(d,J=8.4Hz,2H),2.67(s,3H)ppm;13C NMR(101MHz,CDCl3)δ197.3,191.5,141.2,139.0,129.8,128.8,26.9ppm.
实施例12
氮气氛围下,在一个25mL Schlenk管中加入4-醛基苯甲酸(1.0mmol,150.1mg),Et3N(1.8mmol,182.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入HBpin(1.8mmol,230.4mg)和三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为62%。
1H NMR(400MHz,CDCl3)δ10.14(s,2H),8.06(s,4H)ppm;13C NMR(101MHz,CDCl3)δ191.4,140.0,130.1ppm.
实施例13
氮气氛围下,在一个25mL Schlenk管中加入对苯二甲酸单甲酯(1.0mmol,180.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为82%。
1H NMR(400MHz,CDCl3)δ10.11(s,1H),8.20(d,J=8.4Hz,2H),7.96(d,J=8.4Hz,2H),3.97(s,3H)ppm;13C NMR(101 MHz,CDCl3)δ191.5,166.0,139.1,135.0,130.1,129.4,52.5ppm.
实施例14
氮气氛围下,在一个25mL Schlenk管中加入4-乙烯基苯甲酸(1.0mmol,148.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入HBpin(1.1mmol,140.8mg)和三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为61%。
1H NMR(400MHz,CDCl3)δ9.99(s,1H),7.84(d,J=8.4Hz,2H),7.55(d,J=8.4Hz,2H),6.77(dd,J=17.6,10.8Hz,1H),5.91(d,J=17.6Hz,1H),5.44(d,J=10.8Hz,1H)ppm;13C NMR(101MHz,CDCl3)δ191.7,143.4,135.9,135.7,130.1,126.7,117.4ppm.
实施例15
氮气氛围下,在一个25mL Schlenk管中加入4-乙炔基苯甲酸(1.0mmol,146.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为82%。
1H NMR(400MHz,CDCl3)δ10.01(s,1H),7.84(d,J=8.4Hz,2H),7.63(d,J=8.0Hz,2H),3.31(s,1H)ppm;13C NMR(101MHz,CDCl3)δ191.3,135.9,132.7,129.4,128.3,82.6,81.0ppm.
实施例16
氮气氛围下,在一个25mL Schlenk管中加入2,2-二氟-1,3-苯并二恶茂-5-羧酸(1.0mmol,202.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为71%。
1H NMR(400MHz,CDCl3)δ9.93(s,1H),7.68(dd,J=8.0,1.6Hz,1H),7.61(s,1H),7.24(d,J=8.0Hz,1H)ppm;13C NMR(101MHz,CDCl3)δ189.6,1481,144.6,134.2,133.2,131.6,129.1,128.6,109.7,108.8ppm.
实施例17
氮气氛围下,在一个25mL Schlenk管中加入3-(4-氟苯氧基)苯甲酸(1.0mmol,232.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为85%。
1H NMR(400MHz,CDCl3)δ9.92(s,1H),7.84(d,J=8.4Hz,2H),7.13-7.02(m,6H)ppm;13C NMR(101MHz,CDCl3)δ190.6,163.3,160.9,158.5,150.9,131.9,131.3,122.0,121.9,117.2,116.9,116.6ppm.
实施例18
氮气氛围下,在一个25mL Schlenk管中加入4-溴甲基苯甲酸(1.0mmol,213.9mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为73%。
1H NMR(400MHz,CDCl3)δ10.01(s,1H),7.86(d,J=8.0Hz,2H),7.56(d,J=8.0Hz,2H),4.51(s,2H)ppm;13C NMR(101 MHz,CDCl3)δ191.4,144.2,136.1,130.1,129.6,31.9ppm.
实施例19
氮气氛围下,在一个25mL Schlenk管中加入2-萘甲酸(1.0mmol,172.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为87%。
1H NMR(400MHz,CDCl3)δ10.14(s,1H),8.31(s,1H),7.99-7.88(m,4H),7.65-7.56(m,2H)ppm;13C NMR(101MHz,CDCl3)δ192.2,136.4,134.5,134.0,132.6,129.5,129.1,129.0,128.0,127.0,122.7ppm.
实施例20
氮气氛围下,在一个25mL Schlenk管中加入9-芴酮-2-羧酸(1.0mmol,224.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为75%。
1H NMR(400MHz,DMSO-d6)δ10.04(s,1H),8.17(dd,J=7.6,1.6Hz,1H),8.09-8.01(m,2H),7.99-7.91(m,1H),7.70(m,2H),7.50(m,1H)ppm;13C NMR(101MHz,DMSO-d6)δ192.0,191.9,148.9,142.8,137.1,136.9,135.7,134.1,133.8,130.8,124.3,124.0,122.5,121.8ppm.HRMS(ESI)calcd for C14H8O2Na[M+Na]+:231.0417;found:231.0419.
实施例21
氮气氛围下,在一个25mL Schlenk管中加入4-溴甲基苯甲酸(1.0mmol,306.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为45%。
1H NMR(400MHz,CDCl3)δ10.51(d,J=5.5Hz,1H),8.03-7.94(m,1H),7.51-7.43(m,2H),7.35-7.25(m,10H),6.99-6.96(m,1H)ppm;13C NMR(101 MHz,CDCl3)δ191.7,191.6,141.3,141.0,138.5,138.4,136.2,136.1,134.1,133.9,133.8,133.6,130.6,130.5(5),129.1,128.8,128.7,128.6(6)ppm.
实施例22
氮气氛围下,在一个25mL Schlenk管中加入1-芘羧酸(1.0mmol,246.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×10mL)萃取,柱层析分离得到产物醛类化合物,产率为80%。
1H NMR(400MHz,CDCl3)δ10.67(s,1H),9.26(d,J=9.6Hz,1H),8.28(d,J=8.0Hz,1H),8.23-8.14(m,3H),8.10-8.07(m,2H),8.00(t,J=7.6Hz,1H),7.94(d,J=9.2Hz,1H)ppm;13C NMR(101MHz,CDCl3)δ192.9,135.3,131.1,130.9,130.8,130.6,130.5,130.3,127.2,127.0,126.9,126.7,126.4,124.4,124.3,123.9,122.8ppm.
实施例23
氮气氛围下,在一个25mL Schlenk管中加入4-丙基环己基苯甲酸(1.0mmol,246.2mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为88%。
1H NMR(400MHz,CDCl3)δ9.96(s,1H),7.80(d,J=8.0Hz,2H),7.36(d,J=7.6Hz,2H),2.55(t,J=12.0Hz,1H),1.89(d,J=10.0Hz,4H),1.52-1.19(m,7H),1.10-1.01(m,2H),0.91(t,J=7.2Hz,3H)ppm;13C NMR(101MHz,CDCl3)δ192.0,155.2,134.5,129.9,127.5,44.9,39.5,36.9,33.9,33.3,19.9,14.3ppm.HRMS(ESI)calcd for C16H23O[M+H]+:231.1743;found:231.1737.
实施例24
氮气氛围下,在一个25mL Schlenk管中加入二苯并噻吩-3-羧酸-13C(1.0mmol,229.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为81%。
1H NMR(400MHz,CDCl3)δ10.35(s,0.5H),9.92(s,0.5H),8.60(d,J=4.8Hz,1H),8.23-8.20(m,1H),7.97-7.85(m,3H),7.53-7.49(m,2H)ppm;13C NMR(101MHz,CDCl3)δ191.7,146.1,139.7,136.0(d,J=5.1Hz),134.9,133.5,132.9,127.6,126.9(d,J=4.3Hz),125.1,123.3(dd,J=17.8,4.7Hz),123.0,121.9.ppm.HRMS(ESI)calcd forC12 13CH8OSNa[M+Na]+:236.0222;found:236.0224.
实施例25
氮气氛围下,在一个25mL Schlenk管中加入丙磺舒(1.0mmol,285.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为78%。
1H NMR(400MHz,CDCl3)10.11(s,1H),7.97-8.04(m,4H),3.13(t,J=7.6Hz,4H),1.53-1.59(m,4H),0.88(t,J=7.2Hz,6H)ppm;13C NMR(101MHz,CDCl3)δ190.9,145.4,138.5,130.0,127.5,49.8,21.8,11.0ppm.
实施例26
氮气氛围下,在一个25mL Schlenk管中加入FMOC-(4-氨甲基)苯甲酸(1.0mmol,373.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为82%。
1H NMR(400MHz,CDCl3)δ9.97(s,1H),7.82-7.74(m,4H),7.58(d,J=7.2Hz,2H),7.46-7.26(m,6H),5.24(br,1H),4.49(d,J=6.4Hz,2H),4.42(d,J=6.4Hz,2H),4.20(t,J=6.4Hz,1H)ppm;13C NMR(101 MHz,CDCl3)δ191.8,156.5,145.5,143.8,141.3,135.6,130.1,127.7,127.0,124.9,120.0,66.7,47.3,44.7ppm.
实施例27
氮气氛围下,在一个25mL Schlenk管中加入阿达帕林(1.0mmol,412.2mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为81%。
1H NMR(400MHz,CDCl3)δ10.14(s,1H),8.33(s,1H),8.05-8.00(m,2H),7.96(s,2H),7.83(dd,J=8.4,1.6Hz,1H),7.61(d,J=2.8Hz,1H),7.54(dd,J=8.4,2.4Hz,1H),7.00(d,J=8.4Hz,1H),3.90(s,3H),2.19(s,6H),2.11(s,3H),1.80(s,6H)ppm;13C NMR(101MHz,CDCl3)δ192.1,159.1,142.3,139.1,136.9,134.3,133.8,132.3,131.1,129.9,129.1,126.8,126.0,125.8,125.0,123.2,112.1,55.1,40.6,37.2,37.1,29.1ppm.
氮气氛围下,在一个25mL Schlenk管中加入非布索坦(1.0mmol,316.3mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为82%。
1H NMR(400MHz,CDCl3)δ10.09(s,1H),8.24(s,1H),8.11(d,J=8.8Hz,1H),7.04(d,J=8.8Hz,1H),3.92(d,J=6.4Hz,2H),2.78(s,3H),2.16-2.26(m,1H),1.10(d,J=6.4Hz,6H)ppm;13C NMR(101MHz,CDCl3)δ181.8,170.9,162.9,162.5,132.9,132.7,132.4,125.7,115.2,112.7,103.1,75.8,28.1,19.0,16.2ppm.HRMS(ESI)calcd for C16H16N2O2SNa[M+Na]+:232.0825;found:323.0826.
实施例29
氮气氛围下,在一个25mL Schlenk管中加入1-甲基-3-乙基-4-氯-5-吡唑甲酸(1.0mmol,188.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为74%。
1H NMR(400MHz,CDCl3)δ9.88(s,1H),4.09(s,3H),2.95-2.47(m,2H),1.26(t,J=7.6Hz,3H)ppm;13C NMR(101 MHz,CDCl3)δ178.8,150.2,134.0,116.9,39.8,18.9,12.7ppm.HRMS(ESI)calcd for C7H10ClN2O[M+H]+:173.0476;found:173.0479.
实施例30
氮气氛围下,在一个25mL Schlenk管中加入6-喹啉甲酸(1.0mmol,173.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为72%。
1H NMR(400MHz,CDCl3)δ10.20(s,1H),9.04-9.06(m,1H),8.31-8.34(m,2H),8.23-8.18(m,2H),7.51-7.54(m,1H)ppm;13C NMR(101MHz,CDCl3)δ191.4,153.0,150.8,137.4,134.3,133.5,130.7,127.6,126.6,122.1ppm.
实施例31
氮气氛围下,在一个25mL Schlenk管中加入2-溴-4-甲基噻唑-5-羧酸(1.0mmol,220.9mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为68%。
1H NMR(400MHz,CDCl3)δ10.00(s,1H),2.73(s,3H)ppm;13C NMR(101MHz,CDCl3)δ181.0,161.2,144.0,136.7,16.1ppm.HRMS(ESI)calcd for C5H5BrNOS[M+H]+:205.9270;found:205.9273.
实施例32
氮气氛围下,在一个25mL Schlenk管中加入2-吲哚甲酸(1.0mmol,161.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为79%。
1H NMR(400MHz,CDCl3)δ9.85(s,1H),9.59(br,1H),7.74(d,J=8.4Hz,1H),7.48(d,J=8.4Hz,1H),7.39(t,J=7.6Hz,1H),7.27(m,1H),7.20-7.14(m,1H)ppm;13C NMR(101MHz,CDCl3)δ182.3,138.2,135.9,127.3,127.2(9),123.4,121.2,115.1,112.6ppm.
实施例33
氮气氛围下,在一个25mL Schlenk管中加入1-甲基吲哚-2-甲酸(1.0mmol,175.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为70%。
1H NMR(400MHz,CDCl3)δ9.86(s,1H),7.71(d,J=8.4Hz,1H),7.46-7.33(m,2H),7.21(s,1H),7.18-7.14(m,1H),4.06(s,3H)ppm;13C NMR(101 MHz,CDCl3)δ182.8,140.8,135.7,126.9,126.3,123.3,120.9,117.4,110.3,31.4ppm.
实施例34
氮气氛围下,在一个25mL Schlenk管中加入3-(二氟甲基)-1-甲基-1H-吡唑-4-羧酸((1.0mmol,176.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为74%。
1H NMR(400MHz,CDCl3)δ9.99(s,1H),7.98(s,1H),6.89(t,J=54.0Hz,1H),3.99(s,3H)ppm;13C NMR(101 MHz,CDCl3)δ183.4,146.7(t,J=28.5Hz),134.6,121.6,112.8,110.5,108.1,39.7.ppm.HRMS(ESI)calcd for C6H6F2N2ONa[M+Na]+:183.0340;found:183.0340.
实施例35
氮气氛围下,在一个25mL Schlenk管中加入3-甲基肉桂酸(1.0mmol,162.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为59%。
1H NMR(400MHz,CDCl3):δ9.69(d,J=7.7Hz,1H),7.44(d,J=16.0Hz,1H)7.38-7.24(m,4H),6.70(dd,J=16.0,8.0Hz,1H),2.39(s,3H)ppm;13C NMR(101 MHz,CDCl3)δ193.7,153.0,138.8,133.9,132.1,129.1,128.9,128.3,125.7,21.2ppm.
实施例36
氮气氛围下,在一个25mL Schlenk管中加入3,5-二氟苯乙烯酸(1.0mmol,184.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.5mmol,192mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为70%。
1H NMR(400MHz,CDCl3)δ9.69(d,J=7.2Hz,1H),7.38(d,J=16.0Hz,1H),7.12-7.05(m,2H),6.90(tt,J=8.8,2.4Hz,1H),6.68(dd,J=16.0,7.2Hz,1H)ppm;13C NMR(101MHz,CDCl3)δ192.8,164.6,164.5,162.1,162.0,149.3,137.2,137.1,130.6,111.2,111.1,111.0,110.9,106.5,106.3,106.0ppm.
实施例37
氮气氛围下,在一个25mL Schlenk管中加入布洛芬((1.0mmol,206.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为74%。
1H NMR(400MHz,CDCl3)δ9.66(s,1H),7.21-7.06(m,4H),3.57-3.62(m,1H),2.46(d,J=7.2Hz,2H),1.86(m,1H),1.42(d,J=7.2Hz,3H),0.90(d,J=6.8Hz,6H)ppm;13C NMR(101MHz,CDCl3)δ201.1,141.0,134.8,129.8,128.0,52.6,45.0,30.1,22.3,14.5ppm.
实施例38
氮气氛围下,在一个25mL Schlenk管中加入(S)-2-(6-甲氧基萘-2-基)丙酸((1.0mmol,230.9mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为68%。
1H NMR(400MHz,CDCl3)δ9.73(s,1H),7.70-7.75(m,2H),7.59(s,1H),7.27(d,J=8.8Hz,1H),7.21-7.07(m,2H),3.91(s,3H),3.73-3.78(m,1H),1.51(d,J=7.2Hz,3H)ppm;13C NMR(101MHz,CDCl3)δ201.1,157.8,133.8,132.6,129.2,129.1,127.6,127.0,126.7,119.3,105.6,55.3,52.9,14.6ppm.
实施例39
氮气氛围下,在一个25mL Schlenk管中加入2-茚羧酸(1.0mmol,162.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为62%。
1H NMR(400MHz,CDCl3)δ9.76(s,1H),7.22-7.24(m,2H),7.15-7.17(m,2H),3.36-3.23(m,3H),3.23-3.10(m,2H)ppm;13C NMR(101MHz,CDCl3)δ202.8,141.1,126.8,124.6,50.6,32.9ppm.
实施例40
氮气氛围下,在一个25mL Schlenk管中加入卡洛芬(1.0mmol,273.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为57%。
1H NMR(400MHz,CDCl3)δ9.74(s,1H),8.19(s,1H),7.96(d,J=9.2Hz,2H),7.44-6.95(m,4H),3.79-3.74(m,1H),1.51(d,J=6.8Hz,3H)ppm;13C NMR(101MHz,CDCl3)δ201.2,140.5,138.0,136.1,126.0,125.1,124.1,121.9,121.0,120.2,120.0,111.7,110.4,53.3,14.9ppm.
实施例41
氮气氛围下,在一个25mL Schlenk管中加入4-(4-氯苯基)环己基羧酸(1.0mmol,238.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为78%。
1H NMR(400MHz,CDCl3):δ9.67(s,1H),7.26(d,J=8.2Hz,2H),7.13(d,J=8.2Hz,2H),2.53-2.22(m,2H),2.07(dd,J=46.2,11.0Hz,4H),1.53-1.37(m,4H)ppm;13C NMR(101MHz,CDCl3)δ204.2,145.1,131.8,128.5,128.1,49.8,43.2,32.9,26.2ppm.
实施例42
氮气氛围下,在一个25mL Schlenk管中加入1-(4-氟苯基)环丙烷甲酸(1.0mmol,180.2mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为82%。
1H NMR(400MHz,CDCl3)9.15(s,1H),7.33-7.25(m,2H),7.04(t,J=8.4Hz,2H),1.55-1.58(m,2H),1.37-1.40(m,2H)ppm;13C NMR(101MHz,CDCl3)δ200.5,162.2(d,J=246.6Hz),133.1(d,J=3.4Hz),131.8(d,J=8.1Hz),115.5(d,J=21.3Hz),36.8,15.8ppm.HRMS(ESI)calcd for C10H9FONa[M+Na]+:187.0530;found:187.0529.
实施例43
氮气氛围下,在一个25mL Schlenk管中加入1-苯基环丁基甲酸(1.0mmol,176.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为64%。
1H NMR(400MHz,CDCl3)9.53(s,1H),7.37(t,J=7.6Hz,2H),7.26(t,J=7.2Hz,1H),7.15(d,J=7.6Hz,2H),2.70-2.76(m,2H),2.47-2.34(m,2H),1.89-2.04(m,2H)ppm;13CNMR(101MHz,CDCl3)δ199.4,140.9,128.8,127.0,126.4,57.5,28.3,15.8ppm.
实施例44
氮气氛围下,在一个25mL Schlenk管中加入2-苄基丙烯酸(1.0mmol,162.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入HBpin(1.1mmol,140.8mg)和三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为62%。
1H NMR(400MHz,CDCl3)δ9.58(s,1H),7.49-7.01(m,5H),6.06(d,J=18.8Hz,2H),3.55(s,2H)ppm;13C NMR(101MHz,CDCl3)δ193.8,149.6,138.1,135.0,129.0,128.4,126.3,34.0ppm.
实施例45
氮气氛围下,在一个25mL Schlenk管中加入环丙贝特(1.0mmol,288.0mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为62%。
1H NMR(400MHz,CDCl3)δ9.83(s,1H),7.13(d,J=8.0Hz,2H),6.83(d,J=8.4Hz,2H),2.84(t,J=9.6Hz,1H),1.97-1.92(m,1H),1.78(t,J=8.0Hz,1H),1.43(s,6H)ppm;13CNMR(101MHz,CDCl3)δ203.1,154.6,129.9,129.0,119.4,83.2,60.7,34.7,25.8,21.8,21.7(7)ppm.HRMS(ESI)calcd for C13H14Cl2O2Na[M+Na]+:295.0263;found:295.0260.
实施例46
氮气氛围下,在一个25mL Schlenk管中加入4-甲基苯丙酸(1.0mmol,164.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为61%。
1H NMR(400MHz,CDCl3)δ9.80(s,1H),7.16-6.96(m,4H),2.91(t,J=7.6Hz,2H),2.74(t,J=7.2Hz,2H),2.31(s,3H)ppm;13C NMR(101 MHz,CDCl3)δ201.6,137.2,135.8,129.2,128.1,45.3,27.7,20.9ppm.
实施例47
氮气氛围下,在一个25mL Schlenk管中加入苯丁酸(1.0mmol,164.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为64%。
1H NMR(400MHz,CDCl3)δ9.74(s,1H),7.28(t,J=7.2Hz,2H),7.16-7.21(m,3H),2.65(t,J=7.6Hz,2H),2.45-2.41(m,2H),1.99-1.92(m,2H)ppm;13C NMR(101MHz,CDCl3)δ202.2,141.2,128.4,126.1,43.1,35.0,23.6ppm.
实施例48
氮气氛围下,在一个25mL Schlenk管中加入十一酸(1.0mmol,186.2mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为65%。
1H NMR(400MHz,CDCl3)δ9.76(s,1H),2.43-2.39(m,2H),1.66-1.59(m,2H),1.32-1.26(m,14H),0.88(t,J=6.4Hz,3H)ppm;13C NMR(101MHz,CDCl3)δ202.8,43.9,31.8,29.5,29.4,29.3,29.4,29.1,22.6,22.1,14.0ppm.
实施例49
氮气氛围下,在一个25mL Schlenk管中加入吲哚美辛(1.0mmol,357.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为61%。
1H NMR(400MHz,CDCl3)δ9.70(s,1H),7.66(d,J=8.0Hz,2H),7.47(d,J=8.4Hz,2H),6.92-6.82(m,2H),6.68(dd,J=8.8,2.4Hz,1H),3.82(s,3H),3.71(d,J=2.4Hz,2H),2.37(s,3H)ppm;13C NMR(101MHz,CDCl3)δ190.9,168.2,156.1,139.4,136.4,133.7,131.1,130.9,130.6,129.1,115.0,111.9,110.0,100.9,55.7,39.3,13.3ppm.
实施例50
氮气氛围下,在一个25mL Schlenk管中加入(±)-α-硫辛酸(1.0mmol,357.1mg),1-吡啶-4-哌啶(1.6mmol,259.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为58%。
1H NMR(400MHz,CDCl3)δ9.77(s,1H),3.59-3.55(m,1H),3.31-3.01(m,2H),2.51-2.43(m,3H),1.92-1.89(m,1H),1.74-1.63(m,4H),1.55-1.40(m,2H)ppm;13C NMR(101MHz,CDCl3)δ202.2,56.3,43.7,40.2,38.5,34.7,28.8,21.8ppm.
实施例51
氮气氛围下,在一个25mL Schlenk管中加入亚油酸(1.0mmol,357.1mg),1-吡啶-4-哌啶(1.6mmol,280.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为59%。
1H NMR(400MHz,CDCl3)δ9.76(s,1H),5.40-5.31(m,4H),2.77(t,J=6.3Hz,2H),2.42(td,J=7.4,1.9Hz,2H),2.07-2.02(m,4H),1.65-1.59(m,2H),1.32(m,14H),0.89(t,J=6.7Hz,3H)ppm;13C NMR(101MHz,CDCl3)δ202.7,130.2,130.0,128.1,127.9,43.9,31.5,29.5,29.3,29.2,29.1,29.0,27.2,27.1,25.6,22.5,22.1ppm.
实施例52
氮气氛围下,在一个25mL Schlenk管中加入4-(1,3-二氧代异吲哚啉-2-基)丁酸(1.0mmol,233.1mg),1-吡啶-4-哌啶(1.6mmol,280.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为65%。
1H NMR(400MHz,CDCl3)δ9.78(s,1H),7.86-7.84(m,2H),7.74-7.72(m,2H),3.75(t,J=7.2Hz,2H),2.70-2.42(m,2H),2.06-1.99(m,2H)ppm;13C NMR(101 MHz,CDCl3)δ200.8,168.3,134.0,132.0,123.2,41.0,37.1,21.1ppm.
实施例53
氮气氛围下,在一个25mL Schlenk管中加入D-α-生育酚琥珀酸酯(1.0mmol,233.1mg),1-吡啶-4-哌啶(1.6mmol,280.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为62%。
1H NMR(400MHz,CDCl3)δ9.86(s,1H),2.92(s,4H),2.58(t,J=6.8Hz,2H),2.08(s,3H),2.01(s,3H),2.92(s,3H),1.85-1.70(m,2H),1.58-1.47(m,3H),1.44-1.34(m,4H),1.32-1.02(m,17H),0.87-0.84(m,12H)ppm;13C NMR(101 MHz,CDCl3)δ199.6,170.9,149.5,140.5,126.7,124.9,123.0,117.4,75.0,39.4,38.6,37.4(3),37.4,37.3,32.8,32.7,31.1,28.0,26.2,24.8,24.4,22.7,22.6,21.0,20.6,19.7,19.6,12.9,12.0,11.8ppm.HRMS(ESI)calcd for C33H54O4Na[M+Na]+:537.3914;found:537.3925
实施例54
氮气氛围下,在一个25mL Schlenk管中加入去氢胆酸(1.0mmol,233.1mg),1-吡啶-4-哌啶(1.6mmol,280.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为62%。
1H NMR(400MHz,CDCl3)9.78(s,1H),2.96-2.82(m,3H),2.54-1.93(m,13H),1.90-1.82(m,2H),1.68-1.53(m,2H),1.40-1.25(m,7H),1.08(s,3H),0.85(d,J=6.4Hz,3H)ppm;13C NMR(101MHz,CDCl3)δ211.8,208.9,208.6,202.8,56.8,51.7,48.9,46.7,45.6,45.54,44.9,42.7,41.0,38.5,36.4,35.9,35.4,35.2,27.6,27.3,25.0,21.8,18.6,11.7ppm.
实施例55
氮气氛围下,在一个25mL Schlenk管中加入N-羰苄氧基-L-脯氨酸(1.0mmol,249.1mg),1-吡啶-4-哌啶(1.6mmol,280.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为74%。
1H NMR(400MHz,CDCl3)δ9.58(s,0.5H),9.48(s,0.5H),7.37-7.27(m,5H),5.20-5.13(m,2H),4.31-4.18(m,1H),3.61-3.46(m,2H),2.16-1.81(m,4H)ppm;13C NMR(101 MHz,CDCl3)δ199.9,155.3,154.4,136.4,136.2,128.4,128.0,127.9,67.2,67.1(7),65.2,64.8,47.2,46.6,27.7,26.5,24.4,23.6ppm.
实施例56
氮气氛围下,在一个25mL Schlenk管中加入Fmoc-L-脯氨酸(1.0mmol,337.4mg),1-吡啶-4-哌啶(1.6mmol,280.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为64%。
1H NMR(400MHz,CDCl3)δ9.54(s,0.5H),9.21(s,0.5H),7.75(t,J=7.4Hz,2H),7.60(t,J=6.7Hz,1H),7.52(t,J=8.0Hz,1H),7.44-7.27(m,4H),4.55-4.38(m,2H),4.32-3.94(m,2H),3.58-3.44(m,2H),2.10-1.72(m,4H)ppm;13C NMR(101 MHz,CDCl3)δ199.8,199.7,155.3,154.5,143.8,141.3,127.7,127.1,127.0,125.0,124.9,124.8,124.6,67.4,67.2,65.2,64.7,47.2,47.1(7),46.6,27.7,26.5,24.4,23.5ppm.
实施例57
氮气氛围下,在一个25mL Schlenk管中加入N-Fmoc-N-甲基-L-丙氨酸(1.0mmol,325.1mg),1-吡啶-4-哌啶(1.6mmol,280.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg)和HBpin(1.1mmol,140.8mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为79%。
1H NMR(400MHz,CDCl3)δ9.41(d,J=108.4Hz,1H),7.76(d,J=7.6Hz,2H),7.60-7.50(m,2H),7.40(t,J=7.2Hz,2H),7.31(t,J=7.6Hz,2H),4.57-4.46(m,2H),4.31-4.24(m,2H),2.86(s,3H),1.33-1.11(m,3H)ppm;13C NMR(101 MHz,CDCl3)δ199.5,156.5,143.8,141.4,127.7,127.1,124.9,124.6,120.0,67.7,61.8,61.3,47.3,32.0,11.6,11.1ppm.HRMS(ESI)calcd for C19H19NO3Na[M+Na]+:332.1257;found:332.1260.
实施例58
氮气氛围下,在一个25mL Schlenk管中加入苄氧羰基-N-苄基-Beta-丙氨酸(1.0mmol,313.1mg),Et3N(1.8mmol,182.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入HBpin(1.1mmol,140.8mg)和三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为62%。
1H NMR(400MHz,CDCl3)δ9.69(d,J=38.7Hz,1H),7.66-7.06(m,10H),5.17(s,2H),4.52(s,2H),3.58-3.51(m,2H),2.71-2.59(m,2H)ppm;13C NMR(101MHz,CDCl3)δ200.7,156.2,137.5,136.4,128.6,128.5,128.1,127.9,127.5,51.2,42.8,41.3,40.1ppm.
实施例59
氮气氛围下,在一个25mL Schlenk管中加入(((9H-芴-9-基)甲氧基)羰基)-L-蛋氨酸(1.0mmol,371.1mg),Et3N(1.8mmol,182.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入HBpin(1.1mmol,140.8mg)和三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为40%。
1H NMR(400MHz,CDCl3)δ9.62(s,1H),7.76(d,J=7.6Hz,2H),7.58(d,J=7.6Hz,2H),7.40(t,J=7.6Hz,2H),7.31(t,J=7.6Hz,2H),5.49(br,1H),4.46-4.35(m,2H),4.22(t,J=6.4Hz,1H),2.55-2.19(m,3H),2.12-1.90(m,4H)ppm;13C NMR(101MHz,CDCl3)δ198.4,156.1,143.7,143.6,141.3,127.7,127.1,125.0,120.0,66.9,59.3,47.2,29.7,28.6,15.3ppm.
实施例60
氮气氛围下,在一个25mL Schlenk管中加入Fmoc-O-叔丁基-L-丝氨酸(1.0mmol,383.2mg),Et3N(1.8mmol,182.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入HBpin(1.1mmol,140.8mg)和三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为53%。
1H NMR(400MHz,CDCl3)δ9.63(s,1H),7.77(d,J=7.6Hz,2H),7.63-7.54(m,2H),7.40(t,J=7.6Hz,2H),7.32(t,J=7.6Hz,2H),5.65(d,J=7.6Hz,1H),4.55-4.23(m,4H),3.96(dd,J=9.2,3.2Hz,1H),3.63(dd,J=9.6,4.4Hz,1H),1.16(s,9H)ppm;13C NMR(101MHz,CDCl3)δ199.1,156.6,143.8,141.3,127.7,127.1,125.1,120.0,73.8,67.2,60.5,60.0,47.2,27.2ppm.
实施例61
氮气氛围下,在一个25mL Schlenk管中加入Cbz-β-D-高丙氨酸(1.0mmol,337.1mg),Et3N(1.8mmol,182.2mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入HBpin(1.1mmol,140.8mg)和三氟甲磺酰基吡啶盐PPDP-Tf(1.7mmol,755mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×5mL)萃取,柱层析分离得到产物醛类化合物,产率为54%。
1H NMR(400MHz,CDCl3)δ9.74(s,1H),7.38-7.29(m,5H),5.11-5.01(m,3H),4.24-4.12(m,1H),2.70-2.56(m,2H),1.25(d,J=6.8Hz,3H)ppm;13C NMR(101MHz,CDCl3)δ200.6,155.5,136.4,128.5,128.1,128.0,66.7,50.1,42.9,20.8ppm.
实施例62
氮气氛围下,在一个25mL Schlenk管中加入4-溴苯甲酸(0.3mmol,60.0mg),1-吡啶-4-哌啶(0.48mmol,77.8mg)和2mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(0.51mmol,226.5mg)和DBpin(0.33mmol,42.5mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×3mL)萃取,柱层析分离得到产物醛类化合物,产率为75%。
1H NMR(400MHz,CDCl3)δ9.98(s,0.03H),7.75(d,J=8.4Hz 2H),7.75(d,J=8.0Hz2H)ppm;13C NMR(101MHz,CDCl3)δ190.7(t,J=27.2Hz),135.0,132.4,130.9,129.7.ppm.
实施例63
氮气氛围下,在一个25mL Schlenk管中加入萘普生(0.3mmol,69.1mg),1-吡啶-4-哌啶(0.48mmol,77.8mg)和2mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(0.51mmol,226.5mg)和DBpin(0.33mmol,42.5mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×3mL)萃取,柱层析分离得到产物醛类化合物,产率为69%。
1H NMR(400MHz,CDCl3)δ9.74(s,0.02H),7.75-7.70(m,2H),7.59(s,1H),7.28-7.25(m,1H),7.18-7.12(m,2H),3.91(s,3H),3.75(q,J=7.2Hz,1H),1.51(d,J=7.2Hz,3H)ppm;13C NMR(101MHz,CDCl3)δ200.8,157.9,133.9,132.7,129.2,129.1,127.7,127.0,126.7,119.3,105.6,55.3,52.7(t,J=3.3Hz),14.57.ppm.HRMS(ESI)calcd forC14H14DO2Na[M+H]+:216.1129;found:216.1129.
实施例64
氮气氛围下,在一个25mL Schlenk管中加入环丙贝特(0.3mmol,86.4mg),1-吡啶-4-哌啶(0.48mmol,77.8mg)和2mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(0.51mmol,226.5mg)和DBpin(0.33mmol,42.5mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×3mL)萃取,柱层析分离得到产物醛类化合物,产率为66%。
1H NMR(400MHz,CDCl3)δ9.83(s,0.03H),7.13(d,J=8.4Hz,2H),6.83(d,J=8.4Hz,2H),2.86-2.81(m,1H),2.97-1.76(m,2H),1.43(s,6H)ppm;13C NMR(101 MHz,CDCl3)δ202.9(t,J=28.8Hz),154.6,129.9,129.0,119.4,83.1,60.7,34.8,25.9,21.8(d,J=2.8Hz)ppm.HRMS(ESI)calcd for C13H13DCl2O2Na[M+Na]+:296.0326;found:296.0333.
实施例65
氮气氛围下,在一个25mL Schlenk管中加入非布索坦(0.3mmol,94.8mg),1-吡啶-4-哌啶(0.48mmol,77.8mg)和2mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(0.51mmol,226.5mg)和DBpin(0.33mmol,42.5mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×3mL)萃取,柱层析分离得到产物醛类化合物,产率为84%。
1H NMR(400MHz,CDCl3)δ10.09(s,0.03H),8.24(d,J=2.4Hz,1H),8.12-8.10(m,1H),7.03(d,J=8.8Hz,1H),3.92(d,J=6.4Hz,2H),2.77(s,3H),2.27-2.18(m,1H),1.10(d,J=6.8Hz,6H)ppm;13C NMR(101MHz,CDCl3)δ187.3,170.9,162.9,162.5,133.0,132.5,125.7,115.2,112.7,103.2,75.8,28.1,19.0,16.2.ppm.HRMS(ESI)calcd for C16H16DN2O2S[M+H]+:302.1068;found:302.1068.
实施例66
氮气氛围下,在一个25mL Schlenk管中加入吲哚美辛(0.3mmol,107.1mg),1-吡啶-4-哌啶(0.48mmol,77.8mg)和2mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(0.51mmol,226.5mg)和DBpin(0.33mmol,42.5mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×3mL)萃取,柱层析分离得到产物醛类化合物,产率为47%。
1H NMR(400MHz,CDCl3)δ9.71(s,0.03H),7.67(d,J=8.4Hz,2H),7.48(d,J=8.4Hz,2H),6.94-6.78(m,2H),6.69(dd,J=8.8,2.4Hz,1H),3.82(s,3H),3.72(s,2H),2.38(s,3H)ppm;13C NMR(101 MHz,CDCl3)δ197.7,168.2,156.2,139.5,136.5,133.7,131.2,131.0,130.6,129.2,115.1,111.9,110.0,100.9,55.7,39.2,13.3ppm.HRMS(ESI)calcdfor C19H16DClNO3[M+H]+:343.0954;found:343.0955.
实施例67
氮气氛围下,在一个25mL Schlenk管中加入丙磺舒(0.3mmol,85.5mg),1-吡啶-4-哌啶(0.48mmol,77.8mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(0.51mmol,226.5mg)和DBpin(0.33mmol,42.5mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×3mL)萃取,柱层析分离得到产物醛类化合物,产率为71%。
1H NMR(400MHz,CDCl3)δ10.10(s,0.02H),8.03-7.96(m,4H),3.14-3.11(m,4H),1.61-1.57(m,4H),0.87(t,J=7.6Hz,6H)ppm;13C NMR(101MHz,CDCl3)δ190.6(t,J=27.2Hz),145.5,138.5,130.1,127.6,49.9,21.9,11.1ppm.HRMS(ESI)calcd forC13H18DNO3SNa[M+Na]+:293.1041;found:293.1042.
实施例68
氮气氛围下,在一个25mL Schlenk管中加入阿达帕林(0.3mmol,123.7mg),1-吡啶-4-哌啶(0.48mmol,77.8mg)和5mL二氯甲烷,随后在较短的时间间隔内依次加入三氟甲磺酰基吡啶盐PPDP-Tf(0.51mmol,226.5mg)和DBpin(0.45mmol,58.1mg),搅拌10min。反应结束后,向体系中加入水溶液和二氯甲烷(3×3mL)萃取,柱层析分离得到产物醛类化合物,产率为81%。
1H NMR(400MHz,CDCl3)δ10.14(s,0.03H),8.33(s,1H),8.06-7.99(m,2H),7.96(s,2H),7.83(dd,J=8.4,1.6Hz,1H),7.61(d,J=2.4Hz,1H),7.54(dd,J=8.4,2.4Hz,1H),7.00(d,J=8.4Hz,1H),3.90(s,3H),2.19(s,6H),2.11(s,3H),1.81(s,6H)ppm;13C NMR(101MHz,CDCl3)δ191.7,159.1,142.3,139.1,136.9,134.2,133.7,132.3,131.4,129.9,129.1,126.8,126.0,125.8,125.0,123.2,112.2,55.2,40.6,37.2,37.1,29.1ppm.
本发明实施例1-68中的产物及收率如下表1-表7所示。
表1实施例1-13中的产物以及收率
表1
表2实施例14-25中的原料、产物以及收率
表2
表3实施例26-36中的产物以及收率
表3
表4实施例37-48中的产物以及收率
表4
表5实施例49-56中的产物以及收率
表5
表6实施例87-61中的产物以及收率
表6
表7实施例62-68中的产物以及收率
表7
以上所有实施案例得到的产物均通过1H NMR及13C NMR以及表征得到印证,另外新化合物通过高分辨质谱表征得到印证。
此外,本案发明人还参照前述实施例,以本说明书述及的其它原料、工艺操作、工艺条件进行了试验,并均获得了较为理想的结果。
应当理解,本发明的技术方案不限于上述具体实施案例的限制,凡是在不脱离本发明宗旨和权利要求所保护的范围情况下,根据本发明的技术方案做出的技术变形,均落于本发明的保护范围之内。
Claims (10)
1.一种羧基快速转化为醛基的方法,其特征在于包括:使包含羧酸类化合物、有机碱、三氟甲磺酰基吡啶盐、硼烷类化合物和溶剂的混合反应体系进行反应,制得醛类化合物。
4.根据权利要求1所述的方法,其特征在于:所述有机碱包括吡啶类化合物、三乙胺、N-甲基吗啉、N,N-二异丙基乙胺、1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,4-二氮杂二环[2.2.2]辛烷、2,2,6,6-四甲基哌啶中的任意一种或两种以上的组合;
优选的,所述吡啶类化合物包括吡啶、4-二甲氨基吡啶、1-吡啶-4-哌啶、4-吡咯烷基吡啶、4-吗啉吡啶、N,N-二苯基吡啶-4-胺中的任意一种或两种以上的组合。
5.根据权利要求1所述的方法,其特征在于:所述羧酸类化合物、有机碱、三氟甲磺酰基吡啶盐与硼烷类化合物的摩尔比为1.0∶(1.0~2.2)∶(1.0~2.2)∶(1.0~2.0)。
6.根据权利要求1所述的方法,其特征在于包括:在保护性气氛或者干燥空气气氛中,于0~25℃将羧酸类化合物、有机碱与溶剂混合,获得第一混合物。
7.根据权利要求6所述的方法,其特征在于包括:于0~25℃依次向所述第一混合物加入三氟甲磺酰基吡啶盐、硼烷类化合物形成所述混合反应体系并反应5~60min,制得所述醛类化合物;
和/或,所述制备方法包括:于0~25℃依次向所述第一混合物加入硼烷类化合物、三氟甲磺酰基吡啶盐形成所述混合反应体系并反应5~60min,制得所述醛类化合物。
8.根据权利要求1所述的方法,其特征在于还包括:在所述反应完成后,对所获混合物进行萃取、干燥、分离处理。
9.根据权利要求1所述的方法,其特征在于:所述溶剂包括卤代烷烃类溶剂、醚类溶剂、腈类溶剂、芳烃类溶剂、酮类溶剂、酰胺类溶剂中的任意一种或两种以上的组合。
10.根据权利要求9所述的方法,其特征在于:所述卤代烷烃类溶剂包括二氯甲烷和/或1,2-二氯乙烷;
和/或,所述腈类溶剂包括乙腈;
和/或,所述芳烃类溶剂包括甲苯;
和/或,所述醚类溶剂包括四氢呋喃;
和/或,所述酮类溶剂包括丙酮;
和/或,所述酰胺类溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中的任意一种或两种以上的组合。
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CN115477606B (zh) * | 2022-10-18 | 2024-01-26 | 中国科学院兰州化学物理研究所 | 一种将酯快速转化为炔烃的方法 |
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