- High-Throughput Screening of Reductive Amination Reactions Using Desorption Electrospray Ionization Mass Spectrometry
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This study describes the latest generation of a high-throughput screening system that is capable of screening thousands of organic reactions in a single day. This system combines a liquid handling robot with desorption electrospray ionization (DESI) mass spectrometry (MS) for a rapid reaction mixture preparation, accelerated synthesis, and automated MS analysis. A total of 3840 unique reductive amination reactions were screened to demonstrate the throughputs that are capable with the system. Products, byproducts, and intermediates were all monitored in full-scan mass spectra, generating a complete view of the reaction progress. Tandem mass spectrometry experiments were conducted to verify the identity of the products formed. The amine and electrophile reactivity trends represented in the data match what is expected from theory, indicating that the system accurately models the reaction performance. The DESI results correlated well with those generated using more traditional mass spectrometry techniques like liquid chromatography-mass spectrometry, validating the data generated by the system.
- Cooks, R. Graham,Ferreira, Christina R.,Li, Yangjie,Logsdon, David L.,Paschoal Sobreira, Tiago Jose,Thompson, David H.
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supporting information
p. 1647 - 1657
(2020/10/26)
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- Synthesis of 1,3-Amino Alcohols, 1,3-Diols, Amines, and Carboxylic Acids from Terminal Alkynes
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The half-sandwich ruthenium complexes 1-3 activate terminal alkynes toward anti-Markovnikov hydration and reductive hydration under mild conditions. These reactions are believed to proceed via addition of water to metal vinylidene intermediates (4). The functionalization of propargylic alcohols by metal vinylidene pathways is challenging owing to decomposition of the starting material and catalytic intermediates. Here we show that catalyst 2 can be employed to convert propargylic alcohols to 1,3-diols in high yield and with retention of stereochemistry at the propargylic position. The method is also amenable to propargylic amine derivatives, thereby establishing a route to enantioenriched 1,3-amino alcohol products. We also report the development of formal anti-Markovnikov reductive amination and oxidative hydration reactions to access linear amines and carboxylic acids, respectively, from terminal alkynes. This chemistry expands the scope of products that can be prepared from terminal alkynes by practical and high-yielding metal-catalyzed methods.
- Zeng, Mingshuo,Herzon, Seth B.
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p. 8604 - 8618
(2015/09/15)
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- A highly active catalyst supported molecular sieves-NaHCO3 mixture for the selective and advantageous N-monoalkylation of amines
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Amines are mono-N-alkylated by alkylmesylates in the presence of catalyst supported molecular sieves-NaHCO3 mixture in a regioselective, chemoselective and non-toxic process. Observed chemoselectivity is supported by 'DFT'.
- Das, Asish R.,Medda, Arunima,Singha, Raghunath,Guchhait, Nikhil
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experimental part
p. 841 - 848
(2010/06/01)
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- Iminomalonate as a convenient electrophilic amination reagent for grignard reagents
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Diethyl 2-[N-(p-methoxyphenyl)imino]malonate underwent amination reactions with alkyl Grignard reagents to give N-aklylation products in good yields. The obtained N-alkylation products were readily converted into N-alkyl-panisidines by the oxidative removal of the malonate moiety. The p-methoxyphenyl group was subsequently deprotected to give primary amines.
- Niwa, Yasuki,Takayama, Kazuki,Shimizu, Makoto
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p. 1819 - 1825
(2007/10/03)
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- Electrophilic amination with iminomalonate
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Diethyl N-anisyliminomalonate has been found to be an excellent electrophilic amination reagent for Grignard reagents to give N-alkylated products in good yields, and subsequent air oxidation affords N-alkylanisidines.
- Niwa, Yasuki,Takayama, Kazuki,Shimizu, Makoto
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p. 5473 - 5476
(2007/10/03)
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