Green Synthetic Approaches for Biologically Relevant Heterocycles - Goutam Brahmachari

Green Synthetic Approaches for Biologically Relevant Heterocycles (eBook)

Goutam Brahmachari (Autor)

eBook Download: PDF | EPUB

2014 | 1. Auflage
633 Seiten
Elsevier Reference Monographs (Verlag)
978-0-12-800590-3 (ISBN)

Green Synthetic Approaches for Biologically Relevant Heterocycles reviews this significant group of organic compounds within the context of sustainable methods and processes. Each clearly structured chapter features in-depth coverage of various green protocols for the synthesis of a wide variety of bioactive heterocycles classified on the basis of ring-size and/or presence of heteratoms(s). Techniques covered include microwave heating, ultrasound, ionic liquids, solid phase, solvent-free, heterogeneous catalysis, and aqueous media, along with multi-component reaction strategies. This book also integrates advances in green chemistry research into industrial applications and process developments. Green Synthetic Approaches for Biologically Relevant Heterocycles is an essential resource on green chemistry technologies for academic researchers, R&D professionals, and students working in medicinal, organic, natural product, and agricultural chemistry.

Includes global coverage of a wide variety of green synthetic techniques
Features cutting-edge research in the field of bioactive heterocyclic compounds
Focuses extensively on applications, with numerous examples of biologically relevant heterocycles

Professor (Dr.) Goutam Brahmachari was born at Barala in the district of Murshidabad (West Bengal), India on April 14, 1969. He received his high school degree in scientific studies in 1986 at Barala R. D. Sen High School under the West Bengal Council of Higher secondary Education (WBCHSE). Then he moved to Visva-Bharati (a central University founded by Rabindranath Tagore at Santiniketan, West Bengal, India) to study chemistry at the undergraduate level. After graduating from this University in 1990, Prof. Brahmachari completed his masters in 1992 with specialization in organic chemistry and thereafter received his Ph.D. degree in 1997 in chemistry from the same University. He was appointed as assistant professor of organic chemistry at Visva-Bharati University, Department of Chemistry in 1998, and became associate professor in 2008. In 2011, he became full professor of organic chemistry in the same faculty. At present, he is responsible for teaching courses in organic chemistry, natural products chemistry, and physical methods in organic chemistry. Several students have received their Ph.D. degree under the supervision of Prof. Brahmachari during this period, and couples of research fellows are presently working with him both in the fields of natural products and synthetic organic chemistry. He also serves as a member of the Indian Association for the Cultivation of Science (IACS) and Indian Science Congress Association (ISCA), Kolkata, and as an Editor-in-Chief, Signpost Open Access Journal of Organic and Biomolecular Chemistry. He is the Who's Who in the World-2015 Listee.
Prof. Brahmachari's research interests include (i) isolation, structural determination, and/or detailed NMR study of new natural products from medicinal plants; (ii) synthetic organic chemistry with special emphasis on green chemistry; (iii) semi-synthetic studies with natural products, and (iv) evaluation of biological activities and pharmacological potential of natural and synthetic compounds. With more than sixteen years of teaching experience, he has produced so far nearly 120 publications including original research papers, review articles and invited book chapters in edited books in the field of natural products and organic synthesis from internationally reputed presses. Prof. Brahmachari has authored/edited a number of text and reference books that include Organic Name Reactions: A Unified Approach (Narosa Publishing House, New Delhi; Co-published by Alpha Science International, Oxford, 2006), Chemistry of Natural Products: Recent Trends & Developments (Research Signpost, 2006), Organic Chemistry Through Solved Problems (Narosa Publishing House, New Delhi; Co-published by Alpha Science International, Oxford, 2007), Natural Products: Chemistry, Biochemistry and Pharmacology (Narosa Publishing House, New Delhi; Co-published by Alpha Science International, Oxford, 2009), Handbook of Pharmaceutical Natural Products ? 2 volume-set (Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 2010), Bioactive Natural Products: Opportunities & Challenges in Medicinal Chemistry (World Scientific Publishing Co. Pte. Ltd., Singapore, 2011), Chemistry and Pharmacology of Naturally Occurring Bioactive Compounds (CRC Press, Taylor & Francis group, USA, 2013), and Natural Bioactive Molecules: Impacts & Prospects (Narosa Publishing House, New Delhi; Co-published by Alpha Science International, Oxford, 2014).
He is regularly consulted as a referee by leading international journals including Elsevier, Royal Society of Chemistry, American Chemical Society, Wiley, Taylor & Francis, Springer, Bentham Science, Indian Chemical Society, Korean Chemical Society, Brazilian Chemical Society, Bulgarian Academy of Sciences and so on, and also various financial commissions.
Goutam Brahmachari enjoys Songs of Rabindranath Tagore, and finds interests in Literature as well!

Front Cover 1
Green Synthetic Approaches for Biologically Relevant Heterocycles 4
Copyright 5
Dedication 6
Contents 8
Contributors 14
About the Editor 16
Foreword 18
Preface 20
Chapter 1 - Green Synthetic Approaches for Biologically Relevant Heterocycles: An Overview 22
1. INTRODUCTION 22
2. AN OVERVIEW OF THE BOOK 23
3. CONCLUDING REMARKS 27
Chapter 2 - Synthesis of Bioactive Five- and Six-Membered Heterocycles Catalyzed by Heterogeneous Supported Metals 28
1. INTRODUCTION 28
2. SYNTHESIS OF N-CONTAINING HETEROCYCLES 29
3. SYNTHESIS OF OXYGEN-CONTAINING HETEROCYCLES 49
4. SYNTHESIS OF SULFUR-CONTAINING HETEROCYCLES 57
5. CONCLUDING REMARKS 61
References 61
Chapter 3 - Transition-Metal-Free Synthesis of Benzo-Fused Five- and Six-Membered Heterocycles Employing Arynes 66
1. INTRODUCTION 67
2. SYNTHESIS OF FIVE-MEMBERED HETEROCYCLES 68
3. SYNTHESIS OF SIX-MEMBERED HETEROCYCLES 81
4. SYNTHESIS OF MEDIUM-SIZED HETEROCYCLES 92
5. APPLICATIONS OF THE BENZO-FUSED HETEROCYCLES 93
6. CONCLUDING REMARKS 94
References 94
Chapter 4 - Metal-Catalyzed Routes for the Synthesis of Furocoumarins and Coumestans 98
1. INTRODUCTION 98
2. SYNTHETIC ROUTES TO FUROCOUMARIN DERIVATIVES 99
3. SYNTHETIC ROUTES TO COUMESTAN DERIVATIVES 111
4. CONCLUDING REMARKS 117
Acknowledgments 117
References 117
Chapter 5 - Green Solvents for Eco-friendly Synthesis of Bioactive Heterocyclic Compounds 122
1. INTRODUCTION 122
2. HETEROCYCLIC SYNTHESIS IN SUPERCRITICAL CARBON DIOXIDE 123
3. HETEROCYCLIC SYNTHESIS IN PEG 129
4. HETEROCYCLIC SYNTHESIS IN GLYCEROL 147
5. HETEROCYCLIC SYNTHESIS IN GLUCONIC ACID AQUEOUS SOLUTION 151
6. HETEROCYCLIC SYNTHESIS IN ETHYL LACTATE 154
7. CONCLUDING REMARKS 155
References 155
Chapter 6 - Green Catalytic Synthesis of Heterocyclic Structures Using Carbon Dioxide and Related Motifs 162
1. INTRODUCTION 162
2. BIOLOGICAL IMPORTANCE OF CO2-BASED HETEROCYCLIC COMPOUNDS 163
3. GREEN SYNTHESIS OF 1,3-DIOXOLAN-2-ONES AND 1,3-DIOXAN-2-ONES USING CO2 165
4. GREEN SYNTHESIS OF OXAZOLIDINONES AND OXAZODINANONES USING CO2 172
5. RELATED HETEROCYCLES INCORPORATING CO2 OR RELATED SYNTHONS 175
6. CONCLUDING REMARKS 178
References 179
Chapter 7 - Synthetic Approaches to Small- and Medium-Size Aza-Heterocycles in Aqueous Media 184
1. INTRODUCTION 184
2. THREE-MEMBERED RING—AZIRIDINES 185
3. FOUR-MEMBERED RINGS 186
4. FIVE-MEMBERED RINGS 189
5. SIX-MEMBERED RINGS 197
6. SEVEN-MEMBERED RINGS 200
7. CONCLUDING REMARKS 202
References 202
CHAPTER 8 - Green Synthetic Approaches for

206
1. INTRODUCTION 206
2. SYNTHETIC APPROACHES FOR 2-AMINO-4H-PYRANS AND 2-AMINO-4H-PYRAN-ANNULATED HETEROCYCLES IN WATER AND ETHANOL–WATER MEDIA 207
3. CONCLUDING REMARKS 224
Acknowledgments 225
References 225
Chapter 9 - Sustainable Synthesis of Benzimidazoles, Quinoxalines, and Congeners 230
1. INTRODUCTION 230
2. METHODS OF SYNTHESIS OF BENZIMIDAZOLES/QUINOXALINES USING GREENER STRATEGIES 232
3. CONCLUDING REMARKS 272
References 273
Chapter 10 - Green and Catalytic Methods for .-Lactone Synthesis 278
1. INTRODUCTION 278
2. CONSTRUCTIVE METHODS FOR G-LACTONE STRUCTURE 279
3. FUNCTIONALIZATION OF G-LACTONE STRUCTURES 296
4. CONCLUDING REMARKS 305
References 306
Chapter 11 - Green Synthetic Approaches for Medium Ring-Sized Heterocycles of Biological Interest 312
1. INTRODUCTION 312
2. MICROWAVE- AND ULTRASOUND-ASSISTED SYNTHESIS OF MEDIUM RING-SIZED HETEROCYCLES 315
3. USE OF IONIC LIQUIDS AS REACTION MEDIUM AND CATALYST 323
4. USE OF ENVIRONMENTALLY BENIGN SOLVENTS 325
5. USE OF HETEROGENEOUS CATALYSIS 329
6. FLUOROUS SYNTHESIS 330
7. CONCLUDING REMARKS 331
References 332
Chapter 12 - Organocatalyzed Biginelli Reactions: A Greener Chemical Approach for the Synthesis of Biologically Active 3,4-Dihydropyrimidin-2(1H)-ones/-thiones 338
1. INTRODUCTION 338
2. CLASSES OF ORGANOCATALYSTS USED IN THE BIGINELLI REACTION 341
3. BIOLOGICAL SIGNIFICANCE OF 3,4-DIHYDROPYRIMIDIN-2(1H)-ONES/-THIONES 353
4. CONCLUDING REMARKS 355
ABBREVIATIONS 355
Acknowledgments 356
References 356
Chapter 13 - Photocatalytic Minisci Reaction: A Promising and Eco-friendly Route to Functionalize Heteroaromatics of Biological Interest 360
1. INTRODUCTION 360
2. MINISCI REACTION: A VERSATILE TOOL FOR MEDICINAL CHEMISTRY 361
3. MINISCI REACTION: THE GENERAL MECHANISM 362
4. THE PHOTOCATALYTIC APPROACH 365
5. IS IT A GREEN APPROACH? 368
6. MOLECULAR DYNAMICS STUDIES: TOWARD THE SOLUTION? 369
7. CONCLUDING REMARKS 371
Acknowledgments 371
References 371
Chapter 14 - Organohypervalent Iodine Reagents in the Synthesis of Bioactive Heterocycles 374
1. INTRODUCTION 374
2. ORGANOHYPERVALENT IODINE PROMOTED SYNTHESIS OF BIOACTIVE HETEROCYCLES 378
3. CONCLUDING REMARKS 395
ABBREVIATIONS 395
References 395
Chapter 15 - Porous Catalytic Systems in the Synthesis of Bioactive Heterocycles and Related Compounds 398
1. INTRODUCTION 399
2. POROUS CATALYTIC SYSTEMS 399
3. SYNTHESIS OF BIOACTIVE HETEROCYCLES CATALYZED BY POROUS MATERIALS 401
4. CONCLUDING REMARKS 424
Acknowledgment 424
References 424
Chapter 16 - High-Pressure Cycloaddition Reactions in the Synthesis of Biologically Relevant Heterocycles 430
1. INTRODUCTION 430
2. DIELS–ALDER CYCLOADDITIONS 431
3. DIPOLAR CYCLOADDITIONS 451
4. [2+2] CYCLOADDITIONS 453
5. CONCLUDING REMARKS 453
ABBREVIATIONS 453
References 454
Chapter 17 - Ionic Liquids-Prompted Synthesis of Biologically Relevant Five- and Six-Membered Heterocyclic Skeletons: An Update 458
1. INTRODUCTION 458
2. PROPERTIES OF ILS 460
3. RECENT DEVELOPMENTS IN IONIC LIQUIDS RESEARCH 461
4. APPLICATION OF IONIC LIQUIDS IN HETEROCYCLIC SYNTHESIS 464
5. CONCLUDING REMARKS 505
Acknowledgments 505
References 505
Chapter 18 - Heterocycles-Based Ionic Liquid-Supported Synthesis of Small Organic Molecules 516
1. INTRODUCTION 516
2. IONIC LIQUID-SUPPORTED SYNTHESIS OF SMALL MOLECULES 518
3. IONIC LIQUID-SUPPORTED CARBOHYDRATE SYNTHESIS 528
4. IONIC LIQUID-SUPPORTED PEPTIDE SYNTHESIS 530
5. IONIC LIQUID-SUPPORTED REAGENTS 530
6. IONIC LIQUID-SUPPORTED CATALYSTS 531
7. CONCLUDING REMARKS 533
ABBREVIATIONS 533
References 534
Chapter 19 - Microwave-Induced Synthesis of Heterocycles of Medicinal Interests 538
1. INTRODUCTION 538
2. MICROWAVE IRRADIATION: MECHANISM 546
3. MICROWAVE-INDUCED SYNTHESIS OF HETEROCYCLES OF MEDICINAL INTERESTS 547
4. CONCLUDING REMARKS 574
ABBREVIATIONS 574
References 575
Chapter 20 - Application of Microwave Irradiation in the Synthesis of P-Heterocycles 580
1. INTRODUCTION 580
2. FUNCTIONALIZATION OF CYCLIC PHOSPHINIC ACIDS 581
3. DIELS–ALDER CYCLOADDITIONS, FRAGMENTATION-RELATED PHOSPHORYLATIONS, AND INVERSE WITTIG-TYPE REACTIONS 584
4. PHOSPHA-MICHAEL REACTIONS 585
5. KABACHNIK–FIELDS REACTIONS 587
6. CONCLUDING REMARKS 589
References 589
Chapter 21 - Use of Ultrasound in the Synthesis of Heterocycles of Medicinal Interest 592
1. INTRODUCTION 592
2. HETEROCYCLES OF MEDICINAL INTEREST 597
3. CONCLUDING REMARKS 618
References 619
Index 624

Chapter 1

Green Synthetic Approaches for Biologically Relevant Heterocycles

An Overview

Goutam Brahmachari Laboratory of Natural Products & Organic Synthesis, Department of Chemistry, Visva-Bharati (A Central University), West Bengal, India

Abstract

This chapter is aimed to offer an overview of the present book, and summarizes the contents and subject matter of each chapter with an intention to highlight certain glimpses of the coverage to the readers before they go in depth.

Keywords

Biologically relevant heterocycles; Green synthetic approaches; Overview

Outline

1. Introduction 1

2. An Overview of the Book 2

3. Concluding Remarks 6

1. Introduction

This book entitled Green Synthetic Approaches for Biologically Relevant Heterocycles is an endeavor to present cutting-edge research developments in environment-friendly strategies and techniques for the synthesis of a wide variety of heterocycles and their functionalized derivatives of medicinal interests and helps the reader understand how green chemistry research continues to make significant contributions in the process developments for heterocyclic motifs, in both laboratory and industrial productions, required for the discovery and development of new medicinal entities. The reference is meant for synthetic chemists, natural product chemists, combinatorial chemists, pharmacologists as well as other practitioners, and advanced students in related fields. The book comprising of 20 technical chapters, features authoritative, thorough, and in-depth discussion on the applications of various green techniques/protocols in the synthesis of biologically relevant heterocycles. The book is also an attempt to integrate advances in green chemistry research into industrial applications and process developments.

This introductory chapter (Chapter 1) presents an overview of the book, and summarizes the contents and subject matter of each chapter so as to offer certain glimpses of the coverage of discussion to the readers before they go for detailed study.

2. An Overview of the Book

The present book contains a total of 20 technical chapters—Chapter 2 to 21; this section summarizes the contents and subject matter of each of these chapters.

2.1. Chapter 2

In Chapter 2, Ranu and his group have illustrated the impact of heterogeneous supported metal catalysts toward the development of green synthetic protocols for nitrogen (N), oxygen (O), and sulfur (S) containing five- and six-membered heterocycles. These heterocyclic scaffolds are of continued interest due to their potent bioactivities and applications as therapeutic drugs. Use of heterogeneous catalysts in organic syntheses has already received considerable attention in both industry and academia due to their environmentally friendly properties—heterogeneous catalysts are usually recoverable from the reaction mixture by simple means and can be reused in subsequent reactions. Moreover, heterogeneous supported metals are found to show superior activity than homogeneous counterparts in many reactions as well. The authors screened a wide variety of heterogeneous supported metals involving transition metals (Pd, Cu, Au, and Sn), bimetallic systems (Pt/Ir and Mg/Al) and metal oxides (PdO, CuO, ZnO, and SnO2), and described their useful applications with ample of illustrations. Syntheses of five- membered N-containing heterocycles (such as indoles, oxindoles, and triazoles), O-containing heterocycles (such as furans and benzofurans), and S-containing compounds (benzothiazoles and thiophenes) have been considered whereas among six-membered heterocycles, syntheses of quinilones, quinazolines and quinoxalines, benzodioxanes, benzoxazines and 4H-pyrans have been demonstrated under the influence of the said catalytic systems. The preparations of heterogeneous catalysts, their structures, recyclability, and function with reference to certain significant reactions are discussed in detail. In addition, reaction pathways of several reactions are also discussed. The present discussion in Chapter 2 by Ranu and his group would thus be much helpful to the readers at large and must boost the ongoing research in this direction.

2.2. Chapter 3

Chapter 3 by Kaicharla and Biju is devoted to the transition-metal-free synthesis of benzo-fused five and six-membered heterocycles via unique carbon–carbon and carbon–heteroatom bond-forming reactions employing potential arynes. The authors have offered a comprehensive overview of the syntheses of a variety of biologically relevant heterocycles using the potential of arynes under green and operationally simple procedures. The versatile transition-metal-free applications of arynes include cycloaddition reactions, insertion reactions, and multicomponent reactions for the construction of various heterocycles. As discussed in the present chapter about the advantages of using the aryne route to heterocycles include the synthesis under transition-metal-free conditions, use of cheap and readily available starting materials, the rapid construction of heterocycles in one-step or in one-pot, excellent levels of selectivity, and a broad range of applicability. This illuminating review on arynes chemistry would obviously enrich the readers with these synthetically and biologically useful molecules and also would attract the attention of researchers working in this area.

2.3. Chapter 4

In Chapter 4, Cadierno has offered an update on the metal-catalyzed routes for the synthesis of furocoumarins and coumestans. These scaffolds represent a relevant family of heterocyclic compounds of natural origin with a wide range of biological activities, and are currently of great interest for medicinal applications. Spurred by the principles of green chemistry, chemists at large have now been motivated to develop more selective, economical, and cleaner synthetic transformations. Metal-catalyzed transformations are found to provide the most appealing methodologies to access furocoumarin and coumestan scaffolds in an efficient and atom-economical manner. Throughout this chapter, the author has illustrated the enormous potential of the metal-based approaches for the construction of these heterocycles of biological interest. This field remains open, and the present discussion would boost the ongoing research for new discoveries in this area of interest in the coming years.

2.4. Chapter 5

Dolzhenko and Dolzhenko have presented a comprehensive review on the use of green solvents for eco-friendly synthesis of bioactive heterocyclic compounds in Chapter 5. Use of safer solvents is considered as one of the most significant criteria in green chemistry practice. In the synthesis of biologically active compounds with the aim to improve public health, it is extremely important to minimize impact of this process on the health and nature by choosing solvents, which are nontoxic, easily and completely biodegradable. This chapter is dedicated to the synthesis of heterocyclic compounds of potential medicinal interest using supercritical carbon dioxide and unconventional eco-friendly solvents with good biodegradability property, such as polyethylene glycols (PEGs) and some bio-derived solvents (glycerol, ethyl lactate, and gluconic acid aqueous solution). These reaction media have enormous potential for use in medicinal chemistry with many advantages over conventional organic solvents. It is to be mentioned that the search for new green solvents should ultimately be based on their origin from renewable sources. This overview would surely help the researchers a lot deeply involved in the synthesis of heterocycles using green solvents from supercritical CO2 to PEGs and bio-based solvents.

2.5. Chapter 6

Kleij has provided a comprehensive review on green catalytic synthesis of heterocyclic structures using carbon dioxide and related motifs in Chapter 6. The synthesis of heterocyclic compounds constructed by coupling of carbon dioxide with various reaction partners has recently undergone considerable advancement over the last five years; hence, there are currently a number of relatively green methodologies available for the synthesis of pharmaceutically relevant structures including 1,3-dioxolan-2-ones and 1,3-dioxan-2-ones (cyclic carbonates) and oxazolidinones/oxazodinanones (cyclic carbamates). This carbon source may be regarded as a renewable feed stock having a number of interesting features including cheapness, availability, and low toxicity. Current challenges for its conversion have driven contemporary chemists to design new and improved catalytic strategies that can address the need for cleaner production of a range of base chemicals using renewable sources. The present chapter would boost the ongoing advancement in this...

Erscheint lt. Verlag	17.11.2014
Sprache	englisch
Themenwelt	Naturwissenschaften ► Chemie ► Anorganische Chemie
	Naturwissenschaften ► Chemie ► Organische Chemie
	Technik
ISBN-10	0-12-800590-4 / 0128005904
ISBN-13	978-0-12-800590-3 / 9780128005903

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