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Catalyzed Chemoselective Amide Reduction

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Catalyzed Chemoselective Amide Reduction !" #$ ! $%$$ &' () * ( + ,-% . % . & /0, 1 2 % 3 4 %. 4 ( ( % & ( 4 1 ( 1 5 % . & /0, 2 6 %3 ( 4 4 %7 ( 4 % . 4 8 1 (4 / 9 : !0% . 4 4 4 ( 1 ( 1 (9(; 21 % 4 4 %. 1 ( 1 ( 4 % ! #$ ! <== %% = > ? << < < 9;;,$ 3-"@!A@ !,9@@ ; 3-"@!A@ !,9@@ ## " ( $,@ Ǧ Ǧ ̹ǡ ʹͲͳ͹ ǣSearchingfornewMo(CO)6reactions¡ ǣͻ͹ͺǦͻͳǦ͹͸ͶͻǦͻͳͳǦͷ ǣ ͻ͹ͺǦͻͳǦ͹͸ͶͻǦͻͳʹǦʹ Ǧǡ ʹͲͳ͹ ǣ ǡ Dz dz Abstract Ǥ Ǧ ȋȌ͸Ǧ Ǧ Ǥ Ǧ Ǥ Ǧ ǡǡǤ ǡ ǡǦ ƲǤ ȋȌ͸Ǧ Ǧ ȽǦǤ ǡ Ǥ ǡ Ǥ ǡ ȋ Ͷ Ȃ ͹ȌǤ in situ ǡ ǡ ǡ ͶǡͷǦ Ǥ NǦ Ǥ ǡ NǦ Ǧ ǡ Ǥ Populärvetenskaplig Sammanfattning på Svenska ¡ Ú ¡ Ú Ǥ ¡ ÚÚ¤ ¡Ǥ ÚÚ Ú ¡ Ú¡Ǥ Ú ȋ ʹ ͵Ȍ ¤Ú ǡ Ǥ ¡ ¤ ¡¡ȋȌ͸ ¡ ¡ Ǥ ¡ ¡ Ú ¡ ¡ ¡ Ú ¡Ǥ ȋ Ͷ Ȃ ͹Ȍ ¡ÚǤ ¡¡ ¡ ¡Ǥ¤ ÚÚ ¤¡Ǥ ListofPublications ǡ ǦǤ Ǥ Ǥ I. Chemoselective Reduction of Tertiary Amides under Thermal Control: Formation of either Aldehydes or Amines ǡȗ ǡ ȗ Angewandte Chemie International Editionǡ 2016ǡ 55ǡ Ͷͷ͸ʹǦͶͷ͸͸ II. Transformation of Amides into Highly Functionalized Triazolines ǡ ǡ ǡ ȗ ȗ ACSCatalysisǡ2017ǡ7ǡͳ͹͹ͳǦͳ͹͹ͷ III. Mild Reductive Functionalization of Amides into NǦSulfonylformamidines ǡ ǡ ȗ ȗ ChemistryOpenǡ2017ǡ6ǡͶͺͶǦͶͺ͹ IV. An Efficient OneǦpot Procedure for the Direct Preparationof4,5ǦDihydroisoxazolesfromAmides ǡ ǡ ȗ ȗ AdvancedSynthesisandCatalysisǡ2017ǡ359ǡͳͻͻͲǦͳͻͻͷ V. Facile Preparation of Pyrimidinediones and Thioacrylamides by Reductive Functionalization of Amides ǡᑽ ǡᑽ ȗ ȗ ChemicalCommunicationsǡ2017ǡ53ǡͻͳͷͻǦͻͳ͸ʹ ᑽ Ǥ Papersnotincludedaspartofthisthesis: ChemoselectiveReductionofCarboxamides ǡᑽ ǡᑽǡȗ ǡ ȗ ChemicalSocietyReviewsǡ2016ǡ45ǡ͸͸ͺͷǦ͸͸ͻ͹ ThirdǦGeneration Amino Acid FuranosideǦBased Ligands from ૌǦMannose for the Asymmetric Transfer Hydrogenation of Ketones:CatalystswithanExceptionallyWideSubstrateScope ° ǡǡ ǡ ǡȗ ±ȗ ȗ AdvancedSynthesis&Catalysisǡ2016ǡ358ǡͶͲͲ͸ǦͶͲͳͺ Bimetallic Catalysis: Asymmetric Transfer Hydrogenation of Sterically Hindered Ketones Catalyzed by Ruthenium and Potassium ǡ¡ ȗ ChemCatChemǡ2015ǡ7ǡ͵ͶͶͷǦ͵ͶͶͻ Mo(CO)6 Catalysed Chemoselective Hydrosilylation of Ƚ,ȾǦUnsaturatedAmidesfortheFormationofAllylamines ǡ ǡȗ ǡ ȗ ChemicalCommunicationsǡ2014ǡ50ǡͳͶͷͲͺǦͳͶͷͳͳ RutheniumǦCatalyzed TandemǦIsomerization/Asymmetric TransǦ ferHydrogenationofAllylicAlcohols ǡ ȗ ChemistryǦAEuropeanJournalǡ2014ǡ20ǡͳ͸ͳͲʹǦͳ͸ͳͲ͸ Automated Annotation and Quantification of Metabolites in 1HNMRDataofBiologicalOrigin ǡ ǡ Ǥ %ǡ Úǡ AnalyticalandBioanalyticalChemistryǡ2012ǡ403ǡͶͶ͵ǦͶͷͷ ᑽ Ǥ Contents ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ ¡¤ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ ͳǤ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳ ͳǤͳǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͳ ͳǤʹ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤʹ ͳǤʹǤͳǦ 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ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͵͵ ͵Ǥͳ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͵͵ ͵ǤʹǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͵͸ ͵Ǥ͵ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͵͹ ͵ǤͶ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͶʹ ͶǤ ȋ ȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͶ͵ ͶǤͳ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͶ͵ ͶǤʹǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͶͷ ͶǤ͵ 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ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͸͸ ͹Ǥ ȋȌǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͸͹ ͹Ǥͳ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͸͹ ͹ǤʹǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͸ͺ ͹Ǥ͵ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͹Ͷ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͹ͷ ǣǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͹͸ ǣǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͹͹ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤ͹ͺ ǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤǤͺͳ Abbreviations Ǥͳ Ǥ ͳǡʹǦȋȌ ʹǡʹ̵ǦȋȌǦͳǡͳ̵Ǧ ͳǡͷǦ ͳǡ͵ǦȋȌ ee ʹǦ ʹǦ ǡͳǡͶǦǦʹǡ͸ǦǦ ͵ǡͷǦ ʹǦ ʹǦ ǦǦ ʹǦ ʹǦ ʹǦǦ ʹǦ ʹǡʹǯǦȋȌǦͳǡͳǯǦ ȋȌ ȋȌ pǦ ͳǡͳǡ͵ǡ͵Ǧ ȋȌ 1.Introduction ǯ Ǧ Ǥ Ǣ ǡǡǡǦ Ǥ Ǧ Ǧ Ǥ ǡ Ǧ Ǥ ǡ Ǧ Ǧ ǤʹǦ Ǧ Ǧ Ǧ Ǥ 1.1Amides ǡ Ǥ͵ǡͶǡͷ Ǧ Ǥ Ȃ ǡ ȋ ͳȌǤ͸ǡ͹ Ǧ Ǧ ǡ Ǥ ͳ Figure1.a)Theresonancestabilizationbythenitrogenlonepair,theoriginof thestability.b)Theorbitaloverlapthatcontributestotheplanarconformation oftheamides.c)Orderofstabilityfordifferentcarbonylcompounds. Ǥ ǡ ǡ Ǥͺ NǦǡǦ ǡǤ͵Ǧ Ǧ ȋ ͳȌǤͻ Scheme1.SubstitutionreactionofnonǦplanaramidewithmethanol. 1.2ReductionofAmides Ǥ Ǧ ǡ ǡͳͲ ǡͳͳ ǡͳʹ ͳ͵ͳͶȋ ʹȌǤ ǡǦ Ǥ ʹ Scheme2.Differentproductsformedinthereductionofamidesthrough(a)C–O and(b)C–Nbondcleavage.c)Amidereductionintoenamine. 1.2.1NonǦCatalyticReductionofAmides ǡȋ Ȍ ǡ Ǥͳͷǡͳ͸ Ǧ Ǥͳ͹ ǡ Ǧ Ǥ ǡ Ǧ Ǥͳͺ Ǧ ȋ ͶȌǡ ǡ ǡͳͻʹͲǡʹͳ ʹͲǡʹʹ Ǥ ǡ Ǥ ǡ ǡ ȋ ͵ǡ ǤȌǡ Ǥʹ͵ǡʹͶǡǦ ǡ ȋ Ȍ Ǧ ȋ ͵ȉ ͵ȉʹȌǤ ǡ Ǧinsitu Ǧ ǡ ǡǦ ʹͷ Ǥ ȋʹȌ Ǧ ǡ Ǧ ͳǤʹǤͶ ǦǦǤ ȋ Ǧ Ȍǡʹ͸ ǦǦ ͵ ȋ Ȍǡʹ͹Ǧ ʹͺ Ǥ NǦǦNǦȋȌǡ Ǧ Ǥ ǦǤʹͻ ͵Ͳ Ǧ Ǥ ǡ ȋʹ Ȍʹ ǡ ͳǤʹǤͷǤ 1.2.2CatalyticHydrogenationofAmides Ǧ Ǧ Ǥ͵ͳǡ͵ʹ ǡ Ǧ ǡȋǡǡ Ȍǡ Ǥ͵͵ ǡ Ȃ ǡ ȋ ʹȌǤ͵Ͷ Ǧ Ǧ etal.ȋ ͵ȌǤ͵ͷ ǡ Ǧ Ǣ Ǧ Ǥ Ǥ Scheme 3. Chemoselective hydrogenation of a secondary amide containing an estermoiety. Ͷ 1.2.3CatalyticHydrosilylationofAmides Ǧ Ȃ Ǥ͵͵ǡ͵͸ ǡ ǡ ǡǤǡ Ǥ ʹ ʹǡ ͵ǡͳǡʹǦȋȌ ȋȌǡ ȋȌ͵ ǡ ȋȌʹ ǡ ͵ ǡ ͳǡͳǡ͵ǡ͵Ǧ ȋȌǡȋȌȋ Ȍ ȋ ʹȌǤȂ ǡ Ǥ͵͵ Ǧ ǡǦ Ǧ ǡ ͶǡǦ ͵͹ ǡ Ǧ ͶǤ ǡ ǡ Ǥ ǡ ǡ ȋȌ͵ ǡ Ǧ ͵ͺ ǡ Ͷǡ Ǥ ǡǡ ǡ ǦǤ͵͹ ǡ ǡ Ǥ͵ͻ Figure2.
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