- Exploiting Continuous Processing for Challenging Diazo Transfer and Telescoped Copper-Catalyzed Asymmetric Transformations
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Generation and use of triflyl azide in flow enables efficient synthesis of a range of α-diazocarbonyl compounds, including α-diazoketones, α-diazoamides, and an α-diazosulfonyl ester, via both Regitz-type diazo transfer and deacylative/debenzoylative diazo-transfer processes with excellent yields and offers versatility in the solvent employed, in addition to addressing the hazards associated with handling of this highly reactive sulfonyl azide. Telescoping the generation of triflyl azide and diazo-transfer process with highly enantioselective copper-mediated intramolecular aromatic addition and C-H insertion processes demonstrates that the reaction stream containing the α-diazocarbonyl compound can be obtained in sufficient purity to pass directly over the immobilized copper bis(oxazoline) catalyst without detrimentally impacting the catalyst enantioselectivity.
- Crowley, Daniel C.,Brouder, Thomas A.,Kearney, Aoife M.,Lynch, Denis,Ford, Alan,Collins, Stuart G.,Maguire, Anita R.
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p. 13955 - 13982
(2021/09/02)
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- Structure-Activity Relationship and Biological Investigation of SR18292 (16), a Suppressor of Glucagon-Induced Glucose Production
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Despite a myriad of available pharmacotherapies for the treatment of type 2 diabetes (T2D), challenges still exist in achieving glycemic control. Several novel glucose-lowering strategies are currently under clinical investigation, highlighting the need f
- Cameron, Michael D.,Griffin, Patrick R.,Kamenecka, Theodore M.,Lin, Hua,Lin, Li,Novick, Scott J.,Puigserver, Pere,Ruiz, Claudia,Sharabi, Kfir,Zhu, Di
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supporting information
p. 980 - 990
(2021/02/01)
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- Photocatalyzed cascade Meerwein addition/cyclization of: N -benzylacrylamides toward azaspirocycles
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A visible-light-induced cascade Meerwein addition/cyclization of alkenes involving C-F bond cleavage was developed. This method offers a rapid access to azaspirocyclic cyclohexadienones from N-benzylacrylamides via C-F bond cleavage applying H2O as an external oxygen source, allowing for the incorporation of various aromatic moieties originating from aryldiazonium salts.
- Yuan, Li,Jiang, Sheng-Ming,Li, Zeng-Zeng,Zhu, Yong,Yu, Jian,Li, Lan,Li, Ming-Zhu,Tang, Shi,Sheng, Rui-Rong
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supporting information
p. 2406 - 2410
(2018/04/12)
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- Improved Buchner reaction selectivity in the copper-catalyzed reactions of ethyl 3-arylmethylamino-2-diazo-3-oxopropanoates
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Ethyl 3-alkyl(arylmethyl)amino-2-diazo-3-oxopropanoates (diazo amidoacetates) generate generally both cyclohepta[c]pyrrolones (Buchner products) and β-lactams (1,4-insertion products), and show obvious N-substituent-controlled chemoselectivity between the intramolecular Buchner reaction and aliphatic 1,4-C-H insertion under the catalysis of copper salts. The less steric N-alkyl substituents in the amide moiety generally favor the aliphatic 1,4-C-H insertion, while the more steric N-alkyl substituents generally favor the Buchner reaction. Compared with rhodium and ruthenium-catalyzed conditions, the current copper-catalyzed conditions improved the Buchner reaction selectivity of ethyl 3-alkyl(arylmethyl)amino-2-diazo-3-oxopropanoates.
- Liu, Jing,Tu, Jianzhuo,Yang, Zhanhui,Pak, Chol-Ung,Xu, Jiaxi
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p. 4616 - 4626
(2017/07/11)
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- Structure-Reactivity Relationship in the Frustrated Lewis Pair (FLP)-Catalyzed Hydrogenation of Imines
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The autoinduced, frustrated Lewis pair (FLP)-catalyzed hydrogenation of 16-benzene-ring substituted N-benzylidene-tert-butylamines with B(2,6-F2C6H3)3 and molecular hydrogen was investigated by kinetic analysis. The pKa values for imines and for the corresponding amines were determined by quantum-mechanical methods and provided a direct proportional relationship. The correlation of the two rate constants k1 (simple catalytic cycle) and k2 (autoinduced catalytic cycle) with pKa difference between imine and amine pairs (ΔpKa) or Hammett's σ parameter served as useful parameters to establish a structure-reactivity relationship for the FLP-catalyzed hydrogenation of imines.
- Tussing, Sebastian,Kaupmees, Karl,Paradies, Jan
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p. 7422 - 7426
(2016/05/24)
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- Diazo- And transition-metal-free C-H insertion: A direct synthesis of β-lactams
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Carbene intermediates are very useful species for a range of reactions including C-H insertions and cycloadditions. They are most commonly generated by metal-catalyzed release of nitrogen gas from diazo precursors. Herein, we present a novel C-H insertion
- Gomes, Luis F. R.,Veiros, Ls F.,Maulide, Nuno,Afonso, Carlos A. M.
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supporting information
p. 1449 - 1453
(2015/01/30)
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- Reductive Transformations of Carbonyl Compounds Catalyzed by Rhodium Supported on a Carbon Matrix by using Carbon Monoxide as a Deoxygenative Agent
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An efficient method for the rhodium on carbon matrix catalyzed preparation of secondary and tertiary amines, cyanoesters, and nitriles through the reductive amination/alkylation of carbonyl compounds was developed, including a convenient procedure for the tandem formal reductive addition of acetonitrile to aldehydes. The catalyst could be reused, and at least three consecutive reaction cycles were performed with comparable efficiency. The method was shown to be compatible with functional groups prone to reduction by hydrogen and complex hydrides. Beyond the matrix: An efficient method for the rhodium on carbon matrix catalyzed preparation of secondary and tertiary amines, cyanoesters, and nitriles through the reductive amination/alkylation of carbonyl compounds is developed, including a convenient procedure for the tandem formal reductive addition of acetonitrile to aldehydes. TON=turnover number.
- Yagafarov, Niyaz Z.,Usanov, Dmitry L.,Moskovets, Alexey P.,Kagramanov, Nikolai D.,Maleev, Victor I.,Chusov, Denis
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p. 2590 - 2593
(2015/09/15)
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- Luminescent organogold(III) complexes with long-lived triplet excited states for light-induced oxidative C-H bond functionalization and hydrogen production
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All that glitters is gold: Highly phosphorescent gold(III) complexes (see picture) with extended π-conjugated cyclometalating ligands exhibit rich photophysical and photochemical properties. They act as efficient photocatalysts/photosensitizers for oxidative functionalizations of secondary and tertiary benzylic amines and homogeneous hydrogen production from a water/acetonitrile mixture. Copyright
- To, Wai-Pong,Tong, Glenna So-Ming,Lu, Wei,Ma, Chensheng,Liu, Jia,Chow, Andy Lok-Fung,Che, Chi-Ming
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supporting information; body text
p. 2654 - 2657
(2012/04/17)
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