Astruc D. - Modern arene chemistry (2002)(en)

Contents xi

10.1Introduction 330

	Aims of this Account 330
10.2	The DoM Reaction as a Methodological Tool 332
10.2.1	The N-Cumyl Carboxamide, Sulfonamide, and O-Carbamate DMGs 333
10.2.2	The Lithio Carboxylate and Carboxylate Ester DMGs 334
10.2.3	The Di-tert-Butyl Phosphine Oxide DMG 336

10.3Heteroaromatic Directed ortho Metalation (HetDoM) in Methodological Practice 337

10.3.1	p-Excessive Heteroaromatic Directed ortho Metalation (HetDoM)		337
10.3.1.1	Furans and Thiophenes 337
10.3.1.2	Indoles	339
10.3.2	p-Deficient Heteroaromatic Directed ortho Metalation (HetDoM)		342
10.3.2.1	Pyridines	342

10.4The DoM–Transition Metal Catalyzed Aryl–Aryl Cross-Coupling Symbiosis 344

10.4.1 The Suzuki–Miyaura–DoM Link 345

10.4.2Aryl O-Carbamate and S-Thiocarbamate–Grignard Cross-Coupling

Reactions 346

10.4.3 The DoM–Negishi Cross-Coupling Connection 349

10.4.4DoM–Derived Cross-Coupling Reactions. Synthetic Comparison of Boron, Zinc,

and Magnesium Coupling Partners 350

10.5Beyond DoM: The Directed Remote Metalation (DreM) of Biaryl Amides and O-Carbamates – New Methodologies for Condensed Aromatics and

Heteroaromatics 351

10.5.1Heteroatom-Bridged Biaryl DreM. General Anionic Friedel–Crafts

	Complements for Several Classes of Heterocycles	356
10.6	Interfacing DoM with Emerging Synthetic Methods	359
10.7	Closing Comments 362
	References 363

11Arenetricarbonylchromium Complexes: Ipso, Cine, Tele Nucleophilic Aromatic Substitutions 368

Francoise Rose-Munch and Eric Rose

Abstract 368

11.1Introduction 368

11.1.1	E ects on Arene Reactivity of Cr(CO)3 Coordination			368
11.1.2	Coverage and Definitions	369
11.2	Ipso Nucleophilic Aromatic Substitutions 372
11.2.1	Carbon–Oxygen, –Sulfur and –Selenium Bond Formation				372
11.2.2	Carbon–Nitrogen and Carbon–Phosphorus Bond Formation				378
11.2.3	Carbon–Carbon Bond Formation		383
11.2.4	Carbon–Hydrogen and Carbon–Metal Bond Formation 389
11.3	Cine and Tele Nucleophilic Aromatic Substitutions			392
11.3.1	Cleavage of CaF and CaCl Bonds		392
11.3.2	Cleavage of CaO Bonds	394

xii	Contents
		Cleavage of CaN Bonds		395
11.3.3
11.4		Concluding Remarks		396
		Abbreviations 396
		References	397
12		Activation of Simple Arenes by the CpFeB Group and Applications to the Synthesis of
		Dendritic Molecular Batteries 400
		Didier Astruc, Sylvain Nlate, and Jaime Ruiz
		Abstract	400

12.1Introduction 400

12.2	General Features of the CpFeþ Activation of Arenes	401
12.2.1	Complexation and Decomplexation 401
12.2.2	Solubility, Stability, and General Reactivity Trends	402
12.2.3	Single-Electron Reduction and Oxidation 403

12.2.4Deprotonation 403

12.2.5Reaction of the 19-Electron FeI Complex with O2: Extraordinary Reactivity of

	Naked Superoxide and its Inhibition	404
12.2.6	Nucleophilic Reactions 405
12.2.7	Heterolytic Cleavage of Aryl Ethers	406

12.3CpFeþ-Induced Hexafunctionalization of Hexamethylbenzene for the Synthesis

of Metallo-Stars 406

12.4CpFeþ-Induced Octafunctionalization of Durene in the Synthesis of

Metallodendrimer Precursors 411

12.5CpFeþ-Induced Triallylation of Toluene and Reactivity of the Triallyl Tripod

Towards Transition Metals 413

12.6Nonaallylation of Mesitylene for the Synthesis of Dendritic Precursors of Large Metallodendrimers 414

12.7CpFeþ-Induced Activation of Ethoxytoluene in the One-Pot Synthesis of a Phenol Dendron by Triple-Branching and Synthesis of Organometallic Dendrons 419

12.8Convergent and Divergent Syntheses of Large Ferrocenyl Dendrimers with

Good Redox Stabilities 421

12.9Polyferrocenium Dendrimers: Molecular Batteries? 426

12.10Large Dendrimers Functionalized on their Branches by the Electron-Reservoir

	[FeCp(h6-C6Me6)]þ Groups: A Molecular Battery in Action 428
12.11	Conclusion 429
	References	431
13	Charge-Transfer Effects on Arene Structure and Reactivity 435
	Sergiy V. Rosokha and Jay K. Kochi
	Abstract	435

13.1Introduction 435

13.2Mulliken’s Quantitative Description of Intermolecular (Charge-Transfer) Complexes 436

			Contents	xiii
13.2.1	Short Theoretical Background 436
13.2.2	Quantitative Evaluation of Arenes as Electron Donors	437
13.2.3	Spectral (UV/vis) Probe for the Formation of CT Complexes		438
13.2.4	IR Spectroscopic Studies of Charge-Transfer Complexation		442
13.2.5	Thermodynamics of Charge-Transfer Complexation	443
13.3	Structural Features of Arene Charge-Transfer Complexes		445
13.3.1	Bonding Distance of the Donor/Acceptor Dyad in Arene Complexes 446
13.3.2	Relationship Between Hapticity and Charge Transfer in Arene Complexes 447

13.3.3E ect of Charge Transfer on the Structural Features of Coordinated

	Arenes 448
13.3.3.1	Expansion of the Arene Ring 448
13.3.3.2	p-Bond Localization in the Arene Ring 449

13.3.3.3Loss of Planarity of the Arene Ring and the Transition from p- to s- Binding 451

13.4	Charge-Transfer Activation of Coordinated Arenes 452
13.4.1	Carbon–Hydrogen Bond Activation	453
13.4.2	Nucleophilic/Electrophilic Umpolung	455

13.4.3Modification of the Donor/Acceptor Properties of Coordinated Arene

Ligands 457

13.5CT Complexes as Critical Intermediates in Donor/Acceptor Reactions of

Arenes 460

13.5.1E ects of the Donor/Acceptor Interaction on the ET Dynamics of Arene

	Donors 461
13.5.1.1	Steric Control of the Inner/Outer-Sphere Electron Transfer 461
13.5.1.2	Thermal and Photochemical ET in Strongly Coupled CT Complexes		463
13.5.2	Electron-Transfer Paradigm for Arene Transformation via CT Complexes 465
13.5.3	Electron-Transfer Activation of Electrophilic Aromatic Substitution		469
13.5.4	Structural Pre-organization of the Reactants in CT Complexes 470
13.5.5	CT Complexes in Aromatic Nitration and Nitrosation 472
13.6	Concluding Summary 475
	References	475
14	Oxidative Aryl-Coupling Reactions in Synthesis 479
	Guillaume Lessene and Ken S. Feldman
	Abstract	479

14.1Introduction 479

14.2	Mechanistic Overview 480
14.3	Oxidative Coupling Reactions with Hypervalent Iodine Reagents 484
14.4	Other Reagents for the Oxidative Coupling Reaction 495

14.4.1Iron(III) 495

14.4.2 Vanadium, Thallium, and Lead 499

14.4.3Copper(II) 504

14.4.4 Electrochemical Methods 509

14.4.5 Other Metals 510

xiv	Contents
			513
14.4.6		Non-Metal Mediated Methods
14.5		Phase-Supported Oxidants 515
14.5.1		Reagents Supported on Inorganic Materials		515
14.5.2		Polymer-Supported Hypervalent Iodine Reagents 515
14.6		Control of Atropisomerism	517
14.6.1		Transfer of Chiral Information via the Molecular Backbone 518
14.6.2		Oxidative Coupling of Two Chiral Molecules		524
14.6.3		Stoichiometric Chiral Oxidation Reagents 524
14.6.4		Catalytic Enantioselective Oxidative Coupling		527

14.7Conclusion 534 References 535

15 Oxidative Conversion of Arenols into ortho-Quinols and ortho-Quinone Monoketals – A Useful Tactic in Organic Synthesis 539

Ste´phane Quideau

Abstract 539

15.1Introduction 539

15.1.1 How to Prepare ortho-Quinols and ortho-Quinone Monoketals 540

15.1.2Why Bother with ortho-Quinols and ortho-Quinone Monoketals? 542

15.1.2.1	Synthetic Reactivity of ortho-Quinols and ortho-Quinone Monoketals 542
15.1.2.2	Biosynthetic Implications of ortho-Quinols and ortho-Quinone Monoketals 543

15.1.2.3Biomechanistic Implications of ortho-Quinols and ortho-Quinone Monoketals 545

15.2	Oxidative Dearomatization of ortho-Substituted Arenols 546
15.2.1	Anodic Oxidation 546
15.2.2	Metal-Based Oxidative Activation		548
15.2.3	Halogen-Based Reagents	550
15.3	Synthetic Applications of ortho-Quinols and ortho-Quinone Monoketals 554
15.3.1	Diels–Alder Cycloadditions	554
15.3.2	Photochemical Rearrangements		561
15.3.3	Nucleophilic Substitutions and Additions 563

15.4Conclusion 568 References 568

16 Molecular Switches and Machines Using Arene Building Blocks 574

Hsian-Rong Tseng and J. Fraser Stoddart

Abstract 574

16.1Introduction 574

16.2	From Self-Assembling [2]Catenanes to Electronic Devices 575
16.3	A Hybrid [2]Catenane Switch 580
16.4	A Self-Complexing Molecular Switch	581
16.5	Pseudorotaxane-Based Supramolecular Machines 582
16.6	[2]Rotaxanes and Molecular Shuttles	583
16.7	The Evolution of Photochemically Driven Molecular Switches 589
16.8	Chemically Switchable Pseudorotaxanes 594

Contents xv

16.9	Molecule-Based XOR Logic Gate 596

16.10Conclusions 597 References 597

Index 600

xvi

List of Contributors

Didier Astruc

Laboratoire de Chimie Organique et Organome´tallique

UMR CNRS No. 5802

Universite´ Bordeaux I

F-33405 Talence Cedex France

Margaret M. Boorum

Department of Chemistry

Merkert Chemistry Center

Boston College

Chestnut Hill, MA 02467-3860

U.S.A.

Uwe H. F. Bunz

Department of Chemistry and Biochemistry

The University of South Carolina

Columbia, SC 29208

U.S.A.

Armin de Meijere

Institut fu¨r Organische Chemie Georg-August-Universita¨t Go¨ttingen Tammannstraße 2

D-37077 Go¨ttingen Germany

Franc¸ois Diederich

Laboratorium fu¨r Organische Chemie ETH Ho¨nggerberg

HCI, G 313 CH-8093 Zu¨rich Switzerland

Karl Heinz Do¨tz

Institut fu¨r Organische Chemie und Biochemie Universita¨t Bonn

Gerhard-Domagk-Straße 1 D-53121 Bonn

Germany

Ken S. Feldman

Department of Chemistry

Eberly College of Science

The Pennsylvania State University

152 Davey Laboratory

University Park, PA 16802-6300

U.S.A.

Rainer Haag

Institut fu¨r Organische Chemie Georg-August-Universita¨t Go¨ttingen Tammannstraße 2

D-37077 Go¨ttingen Germany

W. Dean Harman

Department of Chemistry

University of Virginia

Charlottesville, VA 22901

U.S.A.

Christian G. Hartung

Department of Chemistry

Queen’s University

Kingston, ON

K7L 3N6

Canada

John F. Hartwig

Department of Chemistry

Yale University

P.O. Box 208107

New Haven, CT 06520-8107

U.S.A.

Henning Hopf

Institut fu¨r Organische Chemie Technische Universita¨t Braunschweig Hagenring 30

D-38106 Braunschweig Germany

Joseph M. Keane

Department of Chemistry

University of Virginia

Charlottesville, VA 22901

U.S.A.

Jay K. Kochi

Department of Chemistry

University of Houston

University Park

Houston, TX 77204-5003

U.S.A.

Guillaume Lessene

Department of Chemistry

Eberly College of Science

The Pennsylvania State University

152 Davey Laboratory

University Park, PA 16802-6300

U.S.A.

Mogens Brøndsted Nielsen Laboratorium fu¨r Organische Chemie ETH Ho¨nggerberg

HCI, G 313 CH-8093 Zu¨rich Switzerland

Sylvain Nlate

Laboratoire de Chimie Organique et

Organome´tallique

UMR CNRS No. 5802

Universite´ Bordeaux I

F-33405 Talence Cedex

France

Ste´phane Quideau

Laboratoire de Chimie des Substances Ve´ge´tales Centre de Recherche en Chimie Mole´culaire Universite´ Bordeaux I

351, cours de la Libe´ration F-33405 Talence Cedex France

Eric Rose

Laboratoire de Synthe`se Organique et Organome´tallique

UMR CNRS 7611

Universite´ Pierre et Marie Curie Boite Postale 181

Tour 44 – 1er e´tage 4, Place Jussieu

F-75252 Paris Cedex 05 France

List of Contributors	xvii

Franc¸oise Rose-Munch

Laboratoire de Synthe`se Organique et Organome´tallique

UMR CNRS 7611

Universite´ Pierre et Marie Curie Boite Postale 181

Tour 44 – 1er e´tage 4, Place Jussieu

F-75252 Paris Cedex 05 France

Sergiy V. Rosokha

Department of Chemistry

University of Houston

Houston, TX 77204-5003

U.S.A.

Jaime Ruiz

Laboratoire de Chimie Organique et

Organome´tallique

UMR CNRS No. 5802

Universite´ Bordeaux I

F-33405 Talence Cedex

France

Lawrence T. Scott

Department of Chemistry

Merkert Chemistry Center

Boston College

Chestnut Hill, MA 02467

U.S.A.

Victor Snieckus

Department of Chemistry

Queen’s University

Kingston, Ontario K7L 3N6

Canada

Joachim Stendel Jr.

Institut fu¨r Organische Chemie und Biochemie Universita¨t Bonn

Gerhard-Domagk-Straße 1 D-53121 Bonn

Germany

J. Fraser Stoddart

Department of Chemistry and Biochemistry

University of California, Los Angeles

405 Hilgard Avenue

Los Angeles, CA 90095

U.S.A.

Akira Suzuki

Department of Chemistry and Bioscience

Kurashiki University of Science and the Arts

Kurashiki-shi, 712-8505

Japan

xviii	List of Contributors
	Hsian-Rong Tseng	Mark T. Valahovic
	Department of Chemistry and Biochemistry	Department of Chemistry
	University of California,	University of Virginia
	Los Angeles	Charlottesville, VA 22901
	405 Hilgard Avenue	U.S.A.
	Los Angeles, CA 90095
	U.S.A.

1

Arene Chemistry : From Historical Notes to the

State of the Art

Didier Astruc

The History of Benzene

The history of benzene is one of the most intriguing in science. It started in 1825 with the isolation of benzene by Michael Faraday from the condensed phase of pyrolyzed whale oil. Its planar cyclic structure was first proposed in 1861 by the Austrian physicist and physical chemist Johann Josef Loschmidt [1–5]. However, it was only fully understood some 70 years later, around 1930, with the advent of the modern theories of aromaticity, i.e. the theory of molecular orbitals (Hu¨ckel’s theory) [6–8] and the theory of resonance [9–12].

Loschmidt published the cyclic planar structure of benzene together with those of 121 other arene compounds in a unique 54-page booklet entitled Konstitution-Formeln der organischen Chemie in geographischer Darstellung, which constituted a masterpiece of 19th century organic chemistry [1]. An abstract of this book was published by Herman Kopp in Liebigs Jahresbericht in 1861 [2]. Crucially, Loschmidt’s representation of benzene was very close to the present one.

Four years later, in 1865, August Kekule´ proposed another planar cyclic structure, but in which double bonds were alternating with single bonds. In his article published in the Bull. Soc. Chim. Fr. [13], Kekule´ briefly refers to Loschmidt’s formula in a single sentence ‘‘Elle me paraıˆt pre´fe´rable aux modifications propose´es par MM. Loschmidt et Crum-Brown.’’ [10] (It seems to me preferable to the modifications proposed by Loschmidt and Crum-Brown). The strength of Kekule´’s structure (original representation below) is that this type of formalism is still in use today for the representation of arenes because it shows the tetravalency of carbon.

Whereas Loschmidt’s work was not much publicized, Kekule´’s structure of benzene immediately became well known, criticized, and controversial. Various other structures were proposed as substitution on benzene was shown to be easier than addition, which conflicted with the cyclohexatriene structure. Claus and Dewar proposed alternative structures in 1867, and Claus’ formula was adopted by Koener in 1874.

Ladenburg pointed out that the Kekule´ structure does not account for the fact that there is only one ortho-disubstituted benzene as its fixed double bonds should give rise to two isomers. Thus, Ladenburg suggested a prismatic geometry, for which there would also only be three disubstituted isomers as found experimentally for benzene, whereas Kekule´’s cyclohexatriene structure implies four disubstituted isomers. In 1872, Kekule´ answered this

Modern Arene Chemistry. Edited by Didier Astruc

Copyright 8 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 3-527-30489-4

2Arene Chemistry : From Historical Notes to the State of the Art

Johann Josef Loschmidt (1821–1895) attended Prague University, and then at 21 went to Vienna to study first philosophy and mathematics, and then the natural sciences, physics and chemistry. After industrial ventures making potassium nitrate and oxalic acid among other products, he returned

to Vienna as a concierge in the early 1850s, and then became a school teacher. Always attracted by theoretical problems, he is also known for his calculation in 1865 of the number of molecules in one mL of gas (the ‘‘Loschmidt number’’). In 1866, he became Privatdozent at the University

of Vienna, was elected to the Royal Academy of Sciences in 1867, then became Associate Professor and got the honorary degree of Doctor of Philosophy in 1868. He founded the Society of Chemists and Physicists in Vienna (1869), became the Chairman of the Physical Chemistry Institute (1875), Dean of the Faculty of Philosophy (1877), and was elected to the Senate of the faculty (1885). He was a close friend of Josef Stephan and Ludwig Boltzmann, who were the greatest Viennese physicists of their time.