|Table of Contents|

Iron-Catalyzed Oxidative Cleavage of Terminal Alkynes toCarboxylic Acids with Hydrogen Peroxide(PDF)

《南京师大学报(自然科学版)》[ISSN:1001-4616/CN:32-1239/N]

Issue:
2020年02期
Page:
29-33
Research Field:
·化学·
Publishing date:

Info

Title:
Iron-Catalyzed Oxidative Cleavage of Terminal Alkynes toCarboxylic Acids with Hydrogen Peroxide
Author(s):
Yu XingchenXiao YapingHan Wei
School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China
Keywords:
alkyneshydrogen peroxideiron catalysisoxidative cleavagecarboxylic acids
PACS:
O62
DOI:
10.3969/j.issn.1001-4616.2020.02.006
Abstract:
An iron-catalyzed oxidative cleavage of alkynes to corresponding carboxylic acids with hydrogen peroxide as oxidant is reported. Using 4-chlorophenylacetylene(1a)as model substrate to optimize reaction conditions shows that optimal result can be obtained with FeCl2 as the catalyst,H2O2 as the oxidant,and acetic acid as the promoter in acetonitrile-water(3:1)at 50 ℃. Under the optimized reaction conditions,a variety of acetylene compounds have been examined. Terminal arylalkynes provide superior yields with broad functional group compatibility. Preliminary Mechanistic studies have also been preformed.

References:

[1] FLOSS H G,BEALE J M. Biosynthetic studies on antibiotics[J]. Angewandte chemie international edition,1989,28(2):146-177.
[2]BALKENHOHL F,BUSSCHE H C,LANSKY A,et al. Combinatorial synthesis of small organic molecules[J]. Angewandte chemie international edition,1996,35(20):2288-2337.
[3]CHONG J,PIERREL M,ATANASSOVA R,et al. Free and conjugated benzoic acid in tobacco plants and cell cultures induced accumulation upon elicitation of defense responses and role as salicylic acid precursors[J]. Plant physiology,2001,125(1):318-328.
[4]NICOLAOU K C,CHEN J,EDMONDS D,et al. Recent advances in the chemistry and biology of naturally occurring antibiotics[J]. Angewandte chemie international edition,2009,48(4):660-719.
[5]GERBERICH H R,SEAMAN G C. Kirk-Othmer encyclopedia of chemical technology[M]. New York:John Wiley & Sons,2004.
[6]BENZ P,MUNTWYLER R,WOHLGEMUTH R. Chemoenzymatic synthesis of chiral carboxylic acids via nitriles[J]. Journal of chemical technology and biotechnology,2007,82(12):1087-1098.
[7]BAILEY P S. The reactions of ozone with organic compounds[J]. Chemical reviews,1958,58(5):925-1010.
[8]CRIEGEE R. Mechanism of ozonolysis[J]. Angewandte chemie international edition,1975,14(11):745-752.
[9]CARLSEN P H J,KATSUKI T,MARTIN V S,et al. A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compounds[J]. The journal of organic chemistry,1981,46(19):3936-3938.
[10]YUN H,DANISHEFSKY S J. Straightforward synthesis of panaxytriol:an active component of red ginseng[J]. The journal of organic chemistry,2003,68(11):4519-4522.
[11]YUN H,CHOU T C,DONG H,et al. Total synthesis as a resource in drug discovery:the first in vivo uation of panaxytriol and its derivatives[J]. The journal of organic chemistry,2005,70(25):10375-10380.
[12]SRINIVASAN N S,LEE D G. Preparation of 1,2-diketones:oxidation of alkynes by potassium permanganate in aqueous acetone[J]. The journal of organic chemistry,1979,44(9):1574-1574.
[13]ZHONG Y Q,XIAO H Q,YI X Y. Synthesis,structural characterization and catalysis of ruthenium(II)complexes based on 2,5-bis(2’-pyridyl)pyrrole ligand[J]. Dalton transactions,2016,45:18113-18119.
[14]SHAIKH T M,HONG F E. Iron-catalyzed oxidative cleavage of olefins and alkynes to carboxylic acids with aqueous tert-butyl hydroperoxide[J]. Advanced synthesis and catalysis,2011,353(9):1491-1496.
[15]MIYAMOTO K,SEI Y,YAMAGUCHI K,et al. Iodomesitylene-catalyzed oxidative cleavage of carbon-carbon double and triple bonds using m-chloroperbenzoic acid as a terminal oxidant[J]. Journal of the American chemical society,2009,131(4):1382-1383.
[16]MORIARTY R M,PENMASTA R,AWASTHI A K,et al. Mild oxidative cleavage of alkynes using[bis(trifluoroacetoxy)iodo]pentafluorobenzene[J]. The journal of organic chemistry,1988,53(26):6124-6125.
[17]LEE K,KIM Y H,HAN S B,et al. Osmium replica of mesoporous silicate mcm-48:efficient and reusable catalyst for oxidative cleavage and dihydroxylation reactions[J]. Journal of the American chemical society,2003,125(23):6844-6845.
[18]KUMAR K A A,VENKATESWARLU V,VISHWAKARMA R A,et al. A metal-free approach to carboxylic acids by oxidation of alkyl,aryl,or heteroaryl alkyl ketones or arylalkynes[J]. Synthesis,2015,47(20):3161-3168.
[19]BACKVALL J E. Modern oxidation methods[M]. 2nd ed. Wein-herm:Wiley-VCH,2011.
[20]NOYORI R. Pursuing practical elegance in chemical synthesis[J]. Chemical communications,2005,14:1807-1811.
[21]ZHU Z L,ESPENSON J H. Oxidation of alkynes by hydrogen peroxide catalyzed by methylrhenium trioxide[J]. The journal of organic chemistry,1995,60(24):7728-7732.
[22]LIU B B,CHENG L,HU P H,et al. Iron-catalyzed oxidative C-C(vinyl)σ-bond cleavage of allylarenes to aryl aldehydes at room temperature with ambient air[J]. Chemical communications,2019,55:4817-4820.
[23]HU P H,TAN M X,CHENG L,et al. Bio-inspired iron-catalyzed oxidation of alkylarenes enables late-stage oxidation of complex methylarenes to arylaldehydes[J]. Nature communications,2019,10:2425(1-9).
[24]Enthaler S. The iron-catalyzed oxidation of alkynes-1,2-dione formation versus oxidative cleavage—a matter of temperature[J]. ChemCatChem,2011,3(12):1929-1934.

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Last Update: 2020-05-15