19.11 Reactions of Aldehydes and Ketones with Amines
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Part I: Carbonyl-Olefin Metathesis of Norbornene
Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of Arts and Sciences COLUMBIA UNIVERSITY 2016 1 © 2016 Zara Maxine Seibel All Rights Reserved 2 ABSTRACT Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel This thesis details progress towards the development of an organocatalytic carbonyl- olefin metathesis of norbornene. This transformation has not previously been done catalytically and has not been done in practical manner with stepwise or stoichiometric processes. Building on the previous work of the Lambert lab on the metathesis of cyclopropene and an aldehyde using a hydrazine catalyst, this work discusses efforts to expand to the less stained norbornene. Computational and experimental studies on the catalytic cycle are discussed, including detailed experimental work on how various factors affect the difficult cycloreversion step. The second portion of this thesis details the use of chiral cyclopropenimine bases as catalysts for asymmetric Michael reactions. The Lambert lab has previously developed chiral cyclopropenimine bases for glycine imine nucleophiles. The scope of these catalysts was expanded to include glycine imine derivatives in which the nitrogen atom was replaced with a carbon atom, and to include imines derived from other amino acids. i Table of Contents List of Abbreviations…………………………………………………………………………..iv Part I: Carbonyl-Olefin Metathesis…………………………………………………………… 1 Chapter 1 – Metathesis Reactions of Double Bonds………………………………………….. 1 Introduction………………………………………………………………………………. 1 Olefin Metathesis………………………………………………………………………… 2 Wittig Reaction…………………………………………………………………………... 6 Tebbe Olefination………………………………………………………………………... 9 Carbonyl-Olefin Metathesis……………………………………………………………. -
Alkylation by Enamines for Synthesis of Some Heterocyclic Compounds ﻴﺩ
------J. Raf. Sci., Vol. 20, No.2, pp 92- 101, 2009 ------ Alkylation by Enamines for Synthesis of some Heterocyclic Compounds Jasim A. Abdullah Department of Chemistry College of Education Mosul University (Received 25/ 9/ 2008 ; Accepted 13 / 4 / 2009) ABSTRACT Compounds of 4-phenyl-3-butene-2-one (1) and 4-(4-chlorophenyl)-3-butene-2-one (2) were prepared by reaction of benzaldehyde or 4-chlorobenzaldehyde with acetone. Also 1,3-diphenyl-2-chloropropene-1-one (3) was synthesized from the reaction of benzaldehyde with 2-chloroacetophenone through Claisen-Shmidt condensation. The substituted ∆1(9)- octalone-2 (4,5) was prepared by reaction of the compounds (1and2) with cyclohexanone through Michael addition followed by aldol condensation. Compounds (4,5) were reacted with alkyl halide, as 2-chloroacetophenone or 1,3-diphenyl-2-chloropropene-1-one (3), via enamines formation which then hydrolyzed to give compounds (6-9). Compounds (6,7) were reacted with hydrazine , urea and thiourea to afford compounds (10-15) . The structures of all synthesized compounds were confirmed by available physical and spectral means . Keywords : Enamines , Heterocyclic compounds. ــــــــــــــــــــــــــــــــــــــــــــــــــ ﺍﻻﻟﻜﻠﺔ ﺒﻭﺍﺴﻁﺔ ﺍﻷﻴﻨﺎﻤﻴﻨﺎﺕ ﻟﺘﺸﻴﻴﺩ ﺒﻌﺽ ﺍﻟﻤﺭﻜﺒﺎﺕ ﺍﻟﺤﻠﻘﻴﺔ ﻏﻴﺭ ﺍﻟﻤﺘﺠﺎﻨﺴﺔ ﺍﻟﻤﻠﺨﺹ ﺘﻡ ﺘﺤﻀﻴﺭ ﺍﻟﻤﺭﻜﺒﺎﺕ 4-ﻓﻨﻴل-3-ﺒﻴﻭﺘﻴﻥ-2-ﺍﻭﻥ (1) ﻭ4-(4-ﻜﻠﻭﺭﻭﻓﻨﻴل)-3-ﺒﻴﻭﺘﻴﻥ-2-ﺍﻭﻥ (2) ﻤﻥ ﺘﻔﺎﻋل ﺍﻟﺒﻨﺯﺍﻟﺩﻴﻬﻴﺩ ﺃﻭ 4-ﻜﻠﻭﺭﻭﺍﻟﺒﻨﺯﺍﻟﺩﻴﻬﻴﺩ ﻤﻊ ﺍﻻﺴﻴﺘﻭﻥ . ﺤﻀﺭ ﺍﻟﻤﺭﻜﺏ 3,1-ﺜﻨﺎﺌﻲ ﻓﻨﻴل -2-ﻜﻠـﻭﺭﻭﺒﺭﻭﺒﻴﻥ -1-ﺍﻭﻥ (3) ﻤـﻥ ﺘﻔﺎﻋـل ﺍﻟﺒﻨﺯﺍﻟﺩﻴﻬﻴـﺩ ﻤـﻊ -2 9 1 ﻜﻠﻭﺭﻭﺍﺴﻴﺘﻭﻓﻴﻨﻭﻥ ﺒﻭﺴﺎﻁﺔ ﺘﻜﺎﺜﻑ (ﻜﻠﻴﺯﻥ-ﺸﻤﺩﺕ).ﺤﻀﺭﺕ ﻤﻌﻭﻀﺎﺕ ∆ ( ) –ﺍﻭﻜﺘﺎﻟﻭﻥ-2 ﻤﻥ ﺨﻼل ﺘﻔﺎﻋل ﺍﻟﻤﺭﻜﺒﻴﻥ (2,1) ﻤﻊ ﺍﻟﻬﻜﺴﺎﻨﻭﻥ ﺍﻟﺤﻠﻘﻲ ﺒﻭﺴﺎﻁﺔ ﺍﻀﺎﻓﺔ ﻤﺎﻴﻜل ﺍﻟﺘﻲ ﻴﺘﺒﻌﻬﺎ ﺘﻜﺎﺜﻑ ﺍﻻﻟﺩﻭل . -
Pyramidalization/Twisting of the Amide Functional Group Via Remote Steric Congestion Triggered by Metal Coordination Chemical Science
Chemical Volume 8 Number 1 January 2017 Pages 1–810 Science rsc.li/chemical-science ISSN 2041-6539 EDGE ARTICLE Naoya Kumagai, Masakatsu Shibasaki et al. Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination Chemical Science View Article Online EDGE ARTICLE View Journal | View Issue Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by Cite this: Chem. Sci.,2017,8,85 metal coordination† Shinya Adachi, Naoya Kumagai* and Masakatsu Shibasaki* For decades, the planarity of the amide functional group has garnered sustained interest in organic chemistry, enticing chemists to deform its usually characteristic high-fidelity plane. As opposed to the construction of amides that are distorted by imposing rigid covalent bond assemblies, we demonstrate herein the deformation of the amide plane through increased steric bulk in the periphery of the amide moiety, which is induced by coordination to metal cations. A crystallographic analysis revealed that the thus obtained amides exhibit significant pyramidalization and twisting upon coordination to the metals, Received 16th August 2016 while the amide functional group remained intact. The observed deformation, which should be Accepted 21st September 2016 attributed to through-space interactions, substantially enhanced the solvolytic cleavage of the amide, DOI: 10.1039/c6sc03669d Creative Commons Attribution 3.0 Unported Licence. providing compelling evidence that temporary crowding in the periphery -
Catalytic Direct Asymmetric Michael Reactions
ORGANIC LETTERS 2001 Catalytic Direct Asymmetric Michael Vol. 3, No. 23 Reactions: Taming Naked Aldehyde 3737-3740 Donors Juan M. Betancort and Carlos F. Barbas III* The Skaggs Institute for Chemical Biology and the Department of Molecular Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037 [email protected] Received September 5, 2001 ABSTRACT Direct catalytic enantio- and diastereoselective Michael addition reactions of unmodified aldehydes to nitro olefins using (S)-2-(morpholinomethyl)- pyrrolidine as a catalyst are described. The reactions proceed in good yield (up to 96%) in a highly syn-selective manner (up to 98:2) with enantioselectivities approaching 80%. The resulting γ-formyl nitro compounds are readily converted to chiral, nonracemic 3,4-disubstituted pyrrolidines. The Michael reaction is generally regarded as one of the Typically, carbon nucleophiles that contain an active most efficient carbon-carbon bond forming reactions, and methylene center such as malonic acid esters, â-keto esters, studies concerning this reaction have played an important nitroalkanes, etc. have been studied in the Michael reaction. role in the development of modern synthetic organic Carbonyl compounds, and ketones in particular, have gener- chemistry.1 As the demand for optically active compounds ally only been used as donors following their preactivation has soared in recent years, much progress has been made in by conversion into a more reactive species such as enol or the development of asymmetric variants of this reaction, enamine equivalents.5,6 In these cases, additional synthetic providing for the preparation of Michael adducts with high enantiomeric purity.2 Though remarkable advances have been (3) (a) Chataigner, I.; Gennari, C.; Ongeri, S.; Piarulli, U.; Ceccarelli, S. -
Empowering Alcohols As Carbonyl Surrogates for Grignard-Type Reactions
ARTICLE https://doi.org/10.1038/s41467-020-19857-9 OPEN Empowering alcohols as carbonyl surrogates for Grignard-type reactions Chen-Chen Li 1, Haining Wang1, Malcolm M. Sim1, Zihang Qiu 1, Zhang-Pei Chen1, Rustam Z. Khaliullin1 & ✉ Chao-Jun Li 1 The Grignard reaction is a fundamental tool for constructing C-C bonds. Although it is widely used in synthetic chemistry, it is normally applied in early stage functionalizations owing to 1234567890():,; poor functional group tolerance and less availability of carbonyls at late stages of molecular modifications. Herein, we report a Grignard-type reaction with alcohols as carbonyl surro- gates by using a ruthenium(II) PNP-pincer complex as catalyst. This transformation proceeds via a carbonyl intermediate generated in situ from the dehydrogenation of alcohols, which is followed by a Grignard-type reaction with a hydrazone carbanion to form a C-C bond. The reaction conditions are mild and can tolerate a broad range of substrates. Moreover, no oxidant is involved during the entire transformation, with only H2 and N2 being generated as byproducts. This reaction opens up a new avenue for Grignard-type reactions by enabling the use of naturally abundant alcohols as starting materials without the need for pre-synthesizing carbonyls. 1 Department of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, QC H3A 0B8, ✉ Canada. email: [email protected] NATURE COMMUNICATIONS | (2020) 11:6022 | https://doi.org/10.1038/s41467-020-19857-9 | www.nature.com/naturecommunications 1 ARTICLE NATURE COMMUNICATIONS | https://doi.org/10.1038/s41467-020-19857-9 n tandem with the significant advancements of biological and even be successfully applied in synergistic relay reactions29. -
Synthesis of Optically Pure Macroheterocycles with 2,6-Pyridinedicarboxylic and Adipic Acid Fragments from ∆3-Carene
Macrolides Paper Макролиды Статья DOI: 10.6060/mhc190660y Synthesis of Optically Pure Macroheterocycles with 2,6-Pyridinedicarboxylic and Adipic Acid Fragments from ∆3-Carene Marina P. Yakovleva,@ Kseniya S. Denisova, Galina R. Mingaleeva, Valentina A. Vydrina, and Gumer Yu. Ishmuratov Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences, 450054 Ufa, Russia @Corresponding author E-mail: [email protected] Based on the available natural monoterpene ∆3-carene we have developed the synthesis of four optically pure macroheterocycles with ester and dihydrazide fragments through the intermediate 1-((1S,3R)-3-(2-hydroxyethyl- 2,2-dimethylcyclopropyl)propan-2-one using its [2+1]-interaction with dichloranhydrides of adipic or 2,6-pyridinedicarboxylic acids and [1+1]-condensation of the obtained α,ω-diketodiesters with dihydrazides of adipic or 2,6-pyridinedicarboxylic acids. The structure of new compounds was confirmed by IR and NMR spectroscopy and mass spectrometry. Keywords: 3-Carenes, ozonolysis, sodium hypochlorite, macroheterocycles with ester and dihydrazide fragments, [2+1] and [1+1] condensations, synthesis. Синтез оптически чистых макрогетероциклов со сложноэфирными и дигидразидными фрагментами адипиновой и 2,6-пиридиндикарбоновой кислот из D3-карена М. П. Яковлева,@ К. С. Денисова, Г. Р. Мингалеева, В. А. Выдрина, Г. Ю. Ишмуратов Уфимский Институт химии – обособленное структурное подразделение Федерального бюджетного научного учреждения Уфимского федерального исследовательского центра Российской академии -
Reduction of Organic Functional Groups Using Hypophosphites Rim Mouselmani
Reduction of Organic Functional Groups Using Hypophosphites Rim Mouselmani To cite this version: Rim Mouselmani. Reduction of Organic Functional Groups Using Hypophosphites. Other. Univer- sité de Lyon; École Doctorale des Sciences et de Technologie (Beyrouth), 2018. English. NNT : 2018LYSE1241. tel-02147583v2 HAL Id: tel-02147583 https://tel.archives-ouvertes.fr/tel-02147583v2 Submitted on 5 Jun 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THESE de DOCTORAT DE L’UNIVERSITE DE LYON EN COTUTELLE AVEC L'UNIVERSITÉ LIBANAISE opérée au sein de l’Université Claude Bernard Lyon 1 École Doctorale de Chimie-École Doctorale des Sciences et Technologies Discipline : Chimie Soutenue publiquement le 07/11/2018, par Rim MOUSELMANI Reduction of Organic Functional Groups Using Hypophosphites Devant le jury composé de Mme. Micheline DRAYE Université Savoie Mont Blanc Rapporteure M. Mohammad ELDAKDOUKI Université Arabe de Beyrouth Rapporteur Mme. Emmanuelle SCHULZ Université Paris 11 examinatrice M. Abderrahmane AMGOUNE Université Lyon 1 Président M. Mahmoud FARAJ Université Internationale Libanaise examinateur Mme. Estelle MÉTAY Université Lyon 1 Directrice de thèse M. Ali HACHEM Université Libanaise Directeur de thèse M. Marc LEMAIRE Université Lyon 1 Membre invité M. -
Amide Activation: an Emerging Tool for Chemoselective Synthesis
Featuring work from the research group of Professor As featured in: Nuno Maulide, University of Vienna, Vienna, Austria Amide activation: an emerging tool for chemoselective synthesis Let them stand out of the crowd – Amide activation enables the chemoselective modification of a large variety of molecules while leaving many other functional groups untouched, making it attractive for the synthesis of sophisticated targets. This issue features a review on this emerging field and its application in total synthesis. See Nuno Maulide et al., Chem. Soc. Rev., 2018, 47, 7899. rsc.li/chem-soc-rev Registered charity number: 207890 Chem Soc Rev View Article Online REVIEW ARTICLE View Journal | View Issue Amide activation: an emerging tool for chemoselective synthesis Cite this: Chem. Soc. Rev., 2018, 47,7899 Daniel Kaiser, Adriano Bauer, Miran Lemmerer and Nuno Maulide * It is textbook knowledge that carboxamides benefit from increased stabilisation of the electrophilic carbonyl carbon when compared to other carbonyl and carboxyl derivatives. This results in a considerably reduced reactivity towards nucleophiles. Accordingly, a perception has been developed of amides as significantly less useful functional handles than their ester and acid chloride counterparts. Received 27th April 2018 However, a significant body of research on the selective activation of amides to achieve powerful DOI: 10.1039/c8cs00335a transformations under mild conditions has emerged over the past decades. This review article aims at placing electrophilic amide activation in both a historical context and in that of natural product rsc.li/chem-soc-rev synthesis, highlighting the synthetic applications and the potential of this approach. Creative Commons Attribution 3.0 Unported Licence. -
The. Reactions Op Semicarbazones, Thiosbmicarbazonbs
THE. REACTIONS OP SEMICARBAZONES, THIOSBMICARBAZONBS AMD RELATED COMPOUNDS, IMCLTJDIMG THE ACTION OF AMINES ON AMINOCARBOCARBAZONES. A THESIS PRESENTED BY JOHN MCLEAN B.So. IN FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY OF THE UNIVERSITY OF GLASGOW. / MAY *936. THE ROYAL TECHNICAL COLLEGE, GLASGOW. ProQuest Number: 13905234 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 13905234 Published by ProQuest LLC(2019). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 This research was carried out in the Royal Technical College, Glasgow, under the supervision of Professor F.J. Wilson, whose helpful advice was greatly appreciated by the author. CONTENTS. Page General Introduction, PART 1. The Action of Amines on Amino Carhocarbazones. Introduction... ..... ,..................... 4 Benzylamine......... Theoretical.............. 11 ......... Experimental............. 15 Aniline............. Theoretical............ 21 ............. Experimental............ 22 B-Naphthylamine..... Theoretical............... 27 -
S41467-018-07534-X.Pdf
ARTICLE DOI: 10.1038/s41467-018-07534-x OPEN Differentiation between enamines and tautomerizable imines in the oxidation reaction with TEMPO Xiaoming Jie1, Yaping Shang1, Zhe-Ning Chen 1, Xiaofeng Zhang1, Wei Zhuang1 & Weiping Su1 Enamine and imine represent two of the most common reaction intermediates in syntheses, and the imine intermediates containing α-hydrogen often exhibit the similar reactivity to 1234567890():,; enamines due to their rapid tautomerization to enamine tautomers. Herein, we report that the minor structural difference between the enamine and the enamine tautomer derived from imine tautomerization results in the different chemo- and regioselectivity in the reaction of cyclohexanones, amines and TEMPO: the reaction of primary amines furnishes the formal oxygen 1,2-migration product, α-amino-enones, while the reaction of secondary amines under similar conditions generates exclusively arylamines via consecutive dehydrogenation on the cyclohexyl rings. The 18O-labeling experiment for α-amino-enone formation revealed that TEMPO served as oxygen transfer reagent. Experimental and computational studies of reaction mechanisms revealed that the difference in chemo- and regioselectivity could be ascribed to the flexible imine-enamine tautomerization of the imine intermediate con- taining an α-hydrogen. 1 State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou 350002, China. -
Microwave Assisted Synthesis, Spectral and Antimicrobial Evaluation of Hydrazones and Their Metal Complexes
Devendra Kumar et al. / Journal of Pharmacy Research 2012,5(2),830-834 Research Article Available online through ISSN: 0974-6943 http://jprsolutions.info Microwave assisted synthesis, spectral and antimicrobial evaluation of hydrazones and their metal complexes Devendra Kumar ,Shivani Singh,Neelam,Rubeena Akhtar Department of Chemistry, Institute of Basic Sciences,Dr. B. R. Ambedkar University, Khandari Campus, Agra-282002 Received on:19-12-2011; Revised on: 07-01-2012; Accepted on:28-01-2012 ABSTRACT Six new metal complexes of Co (II), Ni (II) and Cu (II) with bis-(furfuryl) adipic acid dihydrazone (FADH) and bis- (2-acetyl thiophene) adipic acid dihydrazone (2-ATADH) have been synthesized under microwave irradiation. The Microwave irradiation method was found remarkably successful and gave higher yield at less reaction time. All the synthesized compounds have been characterized by running their TLC for single spot, repeated melting point determinations, elemental analyses, IR, 1H-NMR and electronic spectral studies. The elemental analyses and spectral analysis results revealed their Metal: Ligand (1:1) stoichiometry. All the synthesized compounds have been screened in vitro for their antibacterial activity against Staphylococcus aureus, Pseudomonas aeruginosa and also for their antifungal activity against Aspergillus niger and Candida albicans. Key words: Synthesis, Microwave irradiation, Spectral, Antibacterial, Antifungal. INTRODUCTION Over the last few years, there has been growing interest in the synthesis of Synthesis of diethyl adipate: 14.6 g (0.1M) adipic acid was dissolved in organic compounds under green or sustainable chemistry such as micro- 20 ml absolute alcohol. To this solution, 3ml conc. H2SO4 was added. The wave irradiation because of increasing environmental consciousness. -
Organic Chemistry/Fourth Edition: E-Text
CHAPTER 17 ALDEHYDES AND KETONES: NUCLEOPHILIC ADDITION TO THE CARBONYL GROUP O X ldehydes and ketones contain an acyl group RC± bonded either to hydrogen or Ato another carbon. O O O X X X HCH RCH RCRЈ Formaldehyde Aldehyde Ketone Although the present chapter includes the usual collection of topics designed to acquaint us with a particular class of compounds, its central theme is a fundamental reaction type, nucleophilic addition to carbonyl groups. The principles of nucleophilic addition to alde- hydes and ketones developed here will be seen to have broad applicability in later chap- ters when transformations of various derivatives of carboxylic acids are discussed. 17.1 NOMENCLATURE O X The longest continuous chain that contains the ±CH group provides the base name for aldehydes. The -e ending of the corresponding alkane name is replaced by -al, and sub- stituents are specified in the usual way. It is not necessary to specify the location of O X the ±CH group in the name, since the chain must be numbered by starting with this group as C-1. The suffix -dial is added to the appropriate alkane name when the com- pound contains two aldehyde functions.* * The -e ending of an alkane name is dropped before a suffix beginning with a vowel (-al) and retained be- fore one beginning with a consonant (-dial). 654 Back Forward Main Menu TOC Study Guide TOC Student OLC MHHE Website 17.1 Nomenclature 655 CH3 O O O O CH3CCH2CH2CH CH2 CHCH2CH2CH2CH HCCHCH CH3 4,4-Dimethylpentanal 5-Hexenal 2-Phenylpropanedial When a formyl group (±CHœO) is attached to a ring, the ring name is followed by the suffix -carbaldehyde.