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    Home > Nature chemistry: Shuttle catalytic synthesis of acyl chloride from unsaturated hydrocarbon without CO and HCl

    Nature chemistry: Shuttle catalytic synthesis of acyl chloride from unsaturated hydrocarbon without CO and HCl

    • Last Update: 2017-06-22
    • Source: Internet
    • Author: User
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    The synthesis of carboxylic acid derivatives from unsaturated hydrocarbons is an important step in the preparation of polymers, drugs, cosmetics and pesticides In industry, carboxylic acid derivatives are often prepared by carbonylation of Reppe, but Reppe reaction is not suitable for laboratory synthesis The main reasons are as follows: (1) toxic gas CO should be used; (2) special devices should be provided to deal with compressed gas; (3) some nucleophiles have low reactivity; (4) different nucleophiles need different catalytic systems Recently, Bill Morandi and his team from the Max Planck Institute published a paper on nature chemistry, reporting on the method of shuttle catalytic synthesis of acyl chloride from unsaturated hydrocarbons Using cheap butyryl chloride instead of CO and HCl in the reaction has a wide range of substrates and high product yield The synthesized active acyl chloride can be further converted into a series of carbonyl derivatives in situ Acyl chloride compounds are usually active and can be further synthesized into amides, ketones, esters and other compounds Bill Morandi and his team envisage that acyl chloride compounds can be obtained from unsaturated hydrocarbons with a wide range of sources by metal catalyzed hydrochlorocarbonylation The acyl chloride obtained will not be treated, and the next reaction will be carried out directly (Fig 1a) Carbonylation of Reppe seems to be able to achieve conversion from unsaturated hydrocarbon to acyl chloride (Fig 1b) In addition, the challenges of small-scale Reppe hydrochlorocarbonylation in the laboratory are: the active acyl chloride products are unstable under severe catalytic conditions; the toxic gas CO and corrosive HCl are needed in the reaction Inspired by the previous shuttle catalytic synthesis of alkylnitriles (Science 351, 832 – 836 (2016)), the author proposed the idea of using simple acyl chloride as acyl chloride group donor to synthesize complex acyl chloride through reversible isobond group exchange under metal catalysis (Fig 1c) The possible mechanism is shown in Fig 1D The reaction undergoes oxidation addition, decarbonylation, β - H elimination, ligand exchange, migration, CO insertion and reduction elimination Figure 1 Conceptual source of shuttle catalytic synthesis of acyl chloride without CO and HCl: in the early stage of nature chemistry experiment, the author selected different small molecules of fatty acyl chloride with cyclododecyne (1) as the substrate, and determined that the cheap, low molecular weight and high activity butyryl chloride (2) was the hydrogen chloride carbonyl donor After a lot of experiments, Pd / xantphos is the best catalytic system With the optimum reaction conditions, the universality of the substrate was studied First of all, the internal alkynes were studied It was found that, due to the effect of steric hindrance, chlorocarbonyl was selectively connected to the side with small steric hindrance of internal alkynes; the selectivity of the internal alkyne products of a-dipolar group was higher than that of β position The study of terminal alkynes shows that alkynes containing other functional groups (such as halogen, alcohol, ester, ketone, nitrile, amine) can carry out this reaction, while large position alkynes and styrene do not react, and the products are mainly branched isomers Then the olefins were studied The products were mainly straight chain isomers The reactivity of end chain olefins was not as good as that of inner ring olefins, but the presence of polar groups could improve the yield of alkenes Figure 2 Reaction conditions and substrate universality of hydrochlorocarbonylation source: nature chemistry next, the author carried out a series of downstream reactions with the obtained acyl chloride Acyl chloride has high reactivity and can be directly synthesized into other carbonyl derivatives in one pot Nucleophiles with high steric hindrance or weak nucleophilic property all react well with it In addition, the nucleophiles containing SP, SP 2, SP 3C were used to react with acyl chloride in Sonogashira, Suzuki and Kumada, respectively The yield of ketone was very good Fig 3 One pot synthesis of carbonyl derivatives source: nature chemistry in addition, acyl chloride containing unsaturated double bond can carry out further electrophilic addition reaction to synthesize some unnatural amino acids or drugs Fig 4 Application source of hydrochlorocarbonylation: nature chemistry Finally, the author proved the isobond conversion of hydrogen and chlorocarbonyl in shuttle catalysis by isotope labeling experiment Figure 5 Source of isotope labeling experiment: nature chemistry summary: Bill Morandi and his team have realized the hydrochlorocarbonylation which is difficult to be effectively carried out by traditional carbonylation reaction with unsaturated hydrocarbon as raw material through shuttle catalytic process In the reaction, cheap and easy to treat butyryl chloride was used instead of CO and HCl as the source of hydrogen and chlorocarbonyl, and commercial catalysts and ligands were used, which opened a new way for the conversion of unsaturated hydrocarbons into a series of carboxylic acids and ketone derivatives Website academic news link: http://www.chembango.com/news/art? Id = 3600
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