- Trideuteromethylation Enabled by a Sulfoxonium Metathesis Reaction
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A conceptually novel sulfoxonium metathesis reaction between TMSOI and cost-effective DMSO-d6 is developed for the efficient generation of a new trideuteromethylation reagent TDMSOI. The new reagent TDMSOI is produced highly efficiently by simply heating a mixture of TMSOI and DMSO-d6 and directly used for subsequent trideuteromethylation in a "one-pot" operation. The preparative power of the new versatile reagent and the "one-pot" protocol is demonstrated by its use to install the ?CD3 moiety into broad functionalities including phenols, thiophenols, acidic amines, and enolizable methylene units in high yield and at a useful level of deuteration (>87% D).
- Shen, Zuyuan,Zhang, Shilei,Geng, Huihui,Wang, Jiarui,Zhang, Xinyu,Zhou, Anqi,Yao, Cheng,Chen, Xiaobei,Wang, Wei
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supporting information
p. 448 - 452
(2019/01/14)
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- Metal-free radical aromatic carbonylations mediated by weak bases
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We report a new method of metal-free alkoxycarbonylation. This reaction involves the generation of aryl radicals from arenediazonium salts by a very weak base (HCO2Na) under mild conditions. Subsequent radical trapping with carbon monoxide and alcohols gives alkyl benzoates. The conditions (metal-free, 1 equiv. base, MeCN, r.t., 3 h) tolerate various functional groups (I, Br, Cl, CF3, SF5, NO2, ester). Mechanistic studies indicate the operation of a radical aromatic substitution mechanism.
- Koziakov, Denis,Jacobi Von Wangelin, Axel
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supporting information
p. 6715 - 6719
(2017/08/22)
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- Cu(ii)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds
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A novel Cu(ii)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.
- Ma, Ran,He, Liang-Nian,Liu, An-Hua,Song, Qing-Wen
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supporting information
p. 2145 - 2148
(2016/02/09)
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- Palladium-catalyzed carbonylations of aryl bromides using paraformaldehyde: Synthesis of aldehydes and esters
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Carbonylation reactions represent useful tools for organic synthesis. However, the necessity to use gaseous carbon monoxide is a disadvantage for most organic chemists. To solve this problem, novel protocols have been developed for conducting palladium-catalyzed reductive carbonylations of aryl bromides and alkoxycarbonylations using paraformaldehyde as an external CO source (CO gas free). Hence, aromatic aldehydes and esters were synthesized in moderate to good yields.
- Natte, Kishore,Dumrath, Andreas,Neumann, Helfried,Beller, Matthias
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supporting information
p. 10090 - 10094
(2015/03/31)
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- N-Acyl and N-sulfonyloxazolidine-2,4-diones are pseudo-irreversible inhibitors of serine proteases
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The synthesis, inhibitory activity and mode of action of oxazolidine-2,4-diones against porcine pancreatic elastase, here used as a model for human neutrophil elastase, are reported. The nature of N-substitution at the oxazolidine-2,4-dione scaffold has large effect on the inhibitory potency against elastase. N-Acyl and N-sulfonyloxazolidine-2,4-diones emerged as potent pseudo-irreversible inhibitors, displaying high second-order rate constants for PPE inactivation. The title compounds were also shown to be potent inhibitors of human neutrophil elastase (HNE) and proteinase-3, and weak inhibitors of human cathepsin G. The results herein presented show that the oxazolidine-2,4-diones represent a new promising class of serine protease inhibitors.
- Santana, Ana Bela,Lucas, Susana D.,Goncalves, Lidia M.,Correia, Henrique F.,Cardote, Teresa A.F.,Guedes, Rita C.,Iley, Jim,Moreira, Rui
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supporting information; experimental part
p. 3993 - 3997
(2012/07/03)
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