The Chemistry of the Morita-Baylis-Hillman Reaction

by Shi, Min; Wang, Fei-jun; Zhao, Mei-xin; Wei, Yin

• ISBN13: 9781849731294
• ISBN10: 1849731292
• Format: Hardcover
• Copyright: 2011-04-04
• Publisher: Royal Society of Chemistry

Summary

Carbon-carbon bond formations and functional group transformations are the most fundamental reactions for the construction of molecular frameworks and are at the forefront of organic chemistry research. The Morita-Baylis-Hillman (MBH) type reactions possess the two most important requirements - atom economy and generation of multi-functional groups. The last decade has seen exponential growth of the MBH reaction and its applications. In fact, it is already one of the most powerful carbon-carbon bond-forming methods widely used in organic synthesis. Since the 1990s, more and more research groups have initiated work on different aspects of the MBH reaction. These have focused on the scope of the substrates, novel catalysts (especially chiral catalysts), reaction mechanisms, and synthetic applications. Consequently, there is now a need for a reference detailing the chemistry of this important reaction. This unique book summarizes the MBH reaction, aza-MBH reaction and asymmetric MBH/aza-MBH reaction including the latest research and mechanistic investigations. It provides a complete overview of MBH-type reactions aimed at synthetic organic chemists of all levels within academia and industry. The chapters cover the; origin and growth of the Morita-Baylis-Hillman reaction; reactant classes and reaction conditions; catalytic mechanisms; achiral and chiral catalytic systems; transformations of functional groups; use of Morita-Baylis-Hillman adducts and derivatives as starting materials to construct compounds with carbocyclic or heterocyclic frameworks, and the applications of the MBH reaction in synthesizing natural products.

Table of Contents

Morita-Baylis-Hillman Reaction	p. 1
Introduction	p. 1
Mechanism of Morita-Baylis-Hillman Reaction	p. 2
Amine-catalyzed Mechanism	p. 2
Phosphine-catalyzed Mechanism	p. 5
Activated Olefins	p. 8
Acrylates	p. 9
Acrylonitriles	p. 12
Allenes, Acetylenes and Dienes	p. 13
Acrylamides	p. 17
Acrolein	p. 20
¿,ß-Unsatyurated Ketones	p. 20
ß-Substituted Activated Olefins	p. 24
Nitroalkenes	p. 25
Vinyl Sulfones, Vinyl Sulfoxides and Vinyl Sulfonates	p. 26
Vinylphosphonates	p. 27
Miscellaneous Activated Olefins	p. 27
Electrophiles	p. 28
Aldehydes	p. 28
Ketones	p. 39
¿-Keto Esters, ß-Keto Lactones, ß-Keto Lactams and Diketones (ß-Keto Carbonyl Compounds)	p. 41
Imines and Iminium Salts	p. 44
Other Electrophiles	p. 48
Multicomponent One-pot Reaction	p. 49
Intramolecular Morita-Baylis-Hillman Reaction	p. 51
Ionic Liquid as Reaction Media	p. 61
References	p. 69
Catalytic Systems for the Morita-Baylis-Hillman Reaction	p. 79
Introduction	p. 79
Amine-catalyzed System	p. 79
Achiral Amine	p. 79
Chiral Amine	p. 104
Cinchona-derived Catalysts	p. 104
Unnatural Tertiary Amines	p. 116
Non-natural Tertiary Amine/Thiourea (Phenol) Catalysts	p. 121
Phosphine-catalyzed System	p. 122
Achiral Phosphine	p. 122
Chiral Phosphine	p. 132
TiCI4-Lewis Acid Mediated Catalyzed System	p. 146
Chalcogenide-Lewis Acid Mediated System	p. 155
Chalcogenide-TiCI4 Mediated System	p. 156
Chalcogeni de-media ted System in the Presence of Other Lewis Acids	p. 163
Substrates Containing a Chalcogenide Group	p. 166
	p. Co-catalyzed
Proline as Co-catalyst	p. 170
(Thio)ureas as Co-catalyst	p. 175
Other Reagents as Co-catalysts	p. 180
Polymer-supported Catalysts for the Morita-Baylis-Hillman Reaction	p. 192
References	p. 198
Transformations of Functional Groups in Morita-Baylis-Hillman Adducts	p. 209
Introduction	p. 209
Transformations of an Hydroxy! Group	p. 209
Esterification and Etherification	p. 209
Halogenation	p. 216
Miscellaneous Transformations	p. 221
Friedel-Crafts Reaction	p. 222
Isomerization	p. 227
Heck Reaction	p. 230
Hydrogenation	p. 233
Diels-Alder Reaction	p. 238
Nucleophilic Addition	p. 242
Carbon Nucleophiles	p. 242
Nitrogen Nucleophiles	p. 260
Oxygen Nucleophiles	p. 270
Sulfur Nucleophiles	p. 274
Phosphorus Nucleophiles	p. 278
Other Nucleophiles	p. 280
Radical Reactions	p. 284
Metathesis Reaction	p. 290
Other Transformations	p. 295
Epoxidation and Aziridination Reactions	p. 295
Michael Addition Reactions	p. 299
Miscellaneous	p. 305
Conclusions	p. 311
References	p. 311
Morita-Baylis-Hillman Adducts or Derivatives for the Construction of Cyclic Frameworks	p. 325
Introduction	p. 325
Synthesis of Cyclic Hydrocarbon Compounds	p. 326
Cyclopropane Ring Systems	p. 326
Five-membered-ring Carbocyclic Compounds	p. 327
Six-membered-ring Carbocyclic Compounds	p. 332
Aromatic Compounds	p. 338
Bridged Compounds	p. 344
Medium-sized-ring Carbocyclic Compounds	p. 350
Synthesis of Oxygen-containing Heterocyclic Compounds	p. 353
Oxiranes	p. 353
b-Lactones	p. 356
s-Butyrolactones	p. 356
Furan-ring Derivatives	p. 362
Pyrans	p. 368
Pyran-2-ones	p. 370
Coumarin Derivatives	p. 376
Medium-sized-ring Oxygen-containing Heterocycles	p. 379
Synthesis of Nitrogen-containing Heterocyclic Compounds	p. 382
Aziridines	p. 382
Azetidines	p. 383
b-Lactams	p. 384
Pyrrole Derivatives	p. 389
Indoles and Indolizines	p. 404
Piperidines and Pyridines	p. 408
Quinolines	p. 414
Medium-sized-ring Nitrogen-containing Heterocycles	p. 428
Construction of Nitrogen Heterocycles Containing Two Nitrogen Atoms	p. 438
Polyheterocyclic Compounds Containing a Nitrogen Atom	p. 441
Synthesis of Other Heterocyclic Compounds	p. 452
References	p. 461
Application of Morita-Baylis-Hillman Reaction for the Synthesis of Natural Products	p. 485
Introduction	p. 485
Acaterin	p. 485
Analogues of N-Benzoyl-syn-phenylisoserine, (S)-ß-Homoserine and (S)Aspartic Acid	p. 486
Asmarines A and B	p. 487
Aza Analogues of the Tricyclic Skeleton of Daphnane and the ABC Ring System of Phorbol	p. 489
N-Boc-dolaproine	p. 492
Borrelidin	p. 492
(2E)-2-Butyloct-2-enal	p. 493
Caribenolide I	p. 494
Clusianone and Polycyclic Polyprenylated Acylphloroglucinols (PPAPs)	p. 494
Cyclic Peptides	p. 497
(-)-(Z)-Deoxypukalide	p. 497
Diversonol	p. 499
Dolichol Analogues	p. 503
Dykellic Acid and Gelastatin Analogues	p. 503
(+)-Efaroxan	p. 505
Epopromycin B	p. 505
Eupomatilone 2	p. 505
Fleursandol®	p. 511
(+)-Frondosin A	p. 514
Furaquinocins	p. 515
(+)-Heliotridine and (-)-Retronecine	p. 517
Luminacin D	p. 519
Mycestericin E	p. 519
Oxyisoterihanine	p. 521
Phaseolinic Acid	p. 521
Pinnatoxin A	p. 523
Salinosporamide A and its Analogues	p. 523
Selenomilfasartan	p. 525
Solanoeclepin A	p. 525
Sordarin Core	p. 527
(-)-Spinosyn A	p. 530
(-)-Spirotryprostatin B	p. 530
Syributins and Syringolides, Spyhydrofurans and Secosyrins	p. 532
Tacamonine	p. 532
Core of Eleutherobin	p. 538
Trioxacarcinosides B	p. 538
Tubelactomicin	p. 540
6-Tuliposide B	p. 542
(R)-Umbelactone	p. 543
References	p. 543
Subject Index	p. 552
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