Preparative Carbohydrate Chemistry

by Hanessian; Stephen

• ISBN13: 9780824798024
• ISBN10: 0824798023
• Edition: 1st
• Format: Hardcover
• Copyright: 1997-01-02
• Publisher: CRC Press

Summary

Detailing commonly used methods and procedures, this reference discusses the reactions and derivative forms of carbohydrates. It covers the formation, cleavage, and reactions of derivatives and illustrates bond-forming reactions of SN2 types, free radicals, chain extensions, and branching. The contents include: sugar derivatives; selected reactions in carbohydrate chemistry; chemical synthesis of oligosaccharides and O-and N -glycosyl compounds; enzymatic synthesis of sialic acid, KDO, and related deoxyulosonic acids, and of oligosaccharides; synthesis of -glycosyl compounds; carbocycles from carbohydrates; and total synthesis of sugars from non-sugars.

Table of Contents

Preface	iii	(8)
Contributors	xi
PART I SUGAR DERIVATES	1	(84)
Stephen Hanessian
1. Synthesis of Isopropylidene, Benzylidene, and Related Acetals	3	(32)
Pierre Calinaud
Jacques Gelas
I. Introduction	3	(3)
II. Methods	6	(9)
III. Experimental Procedures	15	(13)
References	28	(7)
2. Dialkyl Dithioacetals of Sugars	35	(18)
Derek Horton
Peter Norris
I. Introduction	36	(3)
II. Methods	39	(4)
III. Experimental Procedures	43	(7)
References	50	(3)
3. Regioselective Cleavage of O-Benzylidene Acetals to Benzyl Ethers	53	(16)
Per J. Garegg
I. Introduction	54	(3)
II. Regioselective Reductive Cleavage of O-Benzylidene Acetals to Benzyl Ethers	57	(4)
III. Mechanistic Considerations	61	(1)
IV. Experimental Procedures	62	(3)
References	65	(4)
4. Selective O-Substitution and Oxidation Using Stannylene Acetals and Stannyl Ethers	69	(16)
Serge David
I. Introduction	69	(1)
II. Methods	70	(5)
III. Experimental Procedures	75	(7)
References	82	(3)
PART II SELECTED REACTIONS IN CARBOHYDRATE CHEMISTRY	85	(178)
Stephen Hanessian
5. SN2-Type Halogenation and Azidation Reactions with Carbohydrate Triflates	87	(18)
Edith R. Binkley
Roger W. Binkley
I. Triflate Synthesis and Reactivity	88	(2)
II. Introducing Azido and Halogeno Groups by Triflate Displacement	90	(3)
III. Reactions of Carbohydrate Triflates	93	(3)
IV. Carbohydrate Imidazolylsufonates	96	(1)
V. Experimental Procedures	97	(5)
References	102	(3)
6. Direct Halogenation of Carbohydrate Derivates	105	(22)
Walter A. Szarek
Xianqi Kong
I. Introduction	106	(1)
II. General Methods for the Direct Halogenation of Alcohols	107	(9)
III. Experimental Procedures	116	(7)
References	123	(4)
7. Nucleophilic Displacement Reactions of Imidazole-1-Sulfonate Esters	127	(24)
Jean-Michel Vatele
Stephen Hanessian
I. Introduction	127	(3)
II. Methods	130	(6)
III. Experimental Procedures	136	(9)
References	145	(6)
8. Free Radical Deoxygenation of Thiocarbonyl Derivatives of Alcohols	151	(22)
D. H. R. Barton
J. A. Ferreira
J. C. Jaszberenyi
I. Introduction	151	(2)
II. Methods	153	(4)
III. Experimental Procedures	157	(11)
Notes and References	168	(5)
9. Thiazole-Based One-Carbon Extension of Carbohydrate Derivatives	173	(34)
Alessandro Dondoni
Alberto Marra
I. Introduction	174	(1)
II. Methods	174	(14)
III. Experimental Procedures	188	(8)
References	196	(11)
10. Selected Methods for Synthesis of Branched-Chain Sugars	207	(56)
Yves Chapleur
Francoise Chretien
I. Introduction	207	(4)
II. Methods	211	(29)
III. Experimental Procedures	240	(12)
References	252	(11)
PART III CHEMICAL SYNTHESIS OF O- AND N-GLYCOSYL COMPOUNDS, AND OF OLIGOSACCHARIDES	263	(204)
Stephen Hanessian
11. O- and N-Glycopeptides: Synthesis of Selectively Deprotected Building Blocks	265	(18)
Horst Kunz
I. Introduction	265	(3)
II. Methods	268	(5)
III. Experimental Procedures	273	(6)
References	279	(4)
12. Oligosaccharide Synthesis with Trichloroacetimidates	283	(30)
Richard R. Schmidt
Karl-Heinz Jung
I. Introduction	283	(6)
II. The Trichloroacetimidate Method	289	(7)
III. Experimental Procedures	296	(12)
References and Notes	308	(5)
13. Oligosaccharide Synthesis from Glycosyl Fluorides and Sulfides	313	(26)
K. C. Nicolaou
Hiroaki Ueno
I. Introduction	314	(1)
II. Methods	314	(15)
III. Experimental Procedures	329	(7)
References	336	(3)
14. Oligosaccharide Synthesis by n-Pentenyl Glycosides	339	(18)
Bert Frase-Reid
Robert Madsen
I. Introduction	339	(2)
II. Methods	341	(7)
III. Experimental Procedures	348	(6)
References and Notes	354	(3)
15. Chemical Synthesis of Sialyl Glycosides	357	(24)
Akira Hasegawa
Makoto Kiso
I. Introduction	358	(1)
II. Regio- and a-Stereoselective Sialyl Glycoside Syntheses Using Thioglycosides of Sialic Acids in Acetonitrile	359	(5)
III. Applications to Systematic Synthesis of Gangliosides and Sialyloligosaccharides	364	(6)
IV. Experimental Procedures	370	(5)
References	375	(6)
16. Glycoside Synthesis Based on the Remote Activation Concept: An Overview	381	(8)
Stephen Hanessian
I. Introduction	381	(1)
II. The Challenges of the Glycosidic Bond	382	(1)
III. The Remote Activation Concept	383	(3)
IV. New Generations of Glycosyl Donors	386	(1)
References	387	(2)
17. Glycoside and Oligosaccharide Synthesis with Unprotected Glycosyl Donors Based on the Remote Activation Concept	389	(24)
Boliang Lou
Gurijala V. Reddy
Heng Wang
Stephen Hanessian
I. Introduction	390	(1)
II. Glycoside and Oligosaccharide Synthesis Using 3-Methoxy-2-pyridyloxy (MOP) O-Unprotected Glycosyl Donors	391	(7)
III. Experimental Procedures	398	(12)
References	410	(3)
18. Oligosaccharide Synthesis by Remote Activation: O-Protected 3-Methoxy-2-pyridyloxy (MOP) Glycosyl Donors	413	(18)
Boliang Lou
Hoan Khai Huynh
Stephen Hanessian
I. Introduction	414	(1)
II. O-Protected 3-Methoxy-2-pyridyloxy Glycosyl Donors	415	(4)
III. Applications to the Synthesis of T Antigen and Sialyl Lex	419	(3)
IV. Experimental Procedures	422	(5)
References	427	(4)
19. Oligosaccharide Synthesis by Remote Activation: O-Protected Glycosyl 2-thiopyridylcarbonate Donors	431	(18)
Boliang Lou
Hoan Khai Huynh
Stephen Hanessian
I. Introduction	432	(2)
II. Methods: Glycosyl 2-thiopyridylcarbonates (TOPCAT) as Glycosyl Donors	434	(5)
III. Experimental Procedures	439	(8)
References	447	(2)
20. Oligosaccharide Synthesis by Selective Anomeric Activation with MOP- and TOPCAT-Leaving Groups	449	(18)
Boliang Lou
Elisabeth Eckhardt
Stephen Hanessian
I. Introduction	450	(7)
II. Experimental Procedures	457	(7)
References	464	(3)
PART IV ENZYMATIC SYNTHESIS OF SIALIC ACID, KDO, AND RELATED DEOXYULOSONIC ACIDS, AND OF OLIGOSACCHARIDES	467	(38)
Stephen Hanessian
21. Enzymatic Synthesis of Carbohydrates	469	(16)
Claudine Auge
Christine Gautheron-Le Narvor
I. Introduction	469	(2)
II. Methods	471	(7)
III. Experimental Procedures	478	(4)
References	482	(3)
22. Oligosaccharide Synthesis by Enzymatic Glycosidation	485	(20)
Wolfgang Fitz
Chi-Huey Wong
I. Introduction	486	(1)
II. Enzymatic Glycosidation	486	(8)
III. Experimental Procedures	494	(8)
References	502	(3)
PART V SYNTHESIS OF C-GLYCOSYL COMPOUNDS	505	(38)
Stephen Hanessian
23. C-Glycosyl Compounds from Free Radical Reactions	507	(20)
Bernd Giese
Heinz-Georg Zeitz
I. Introduction	507	(3)
II. Intermolecular Methods	510	(6)
III. Intramolecular Methods	516	(1)
IV. Experimental Procedures	517	(7)
References	524	(3)
24. Synthesis of Glycosylarenes	527	(16)
Keisuke Suzuki
Takashi Matsumoto
I. Introduction	528	(2)
II. Methods	530	(5)
III. Experimental Procedures	535	(6)
References	541	(2)
PART VI CARBOCYCLES FROM CARBOHYDRATES	543	(50)
Stephen Hanessian
25. Functionalized Carbocylic Derivatives from Carbohydrates: Free Radical and Organometallic Methods	545	(24)
T. V. RajanBabu
I. Introduction	546	(1)
II. Cyclopentanes	546	(8)
III. Cyclohexanes	554	(1)
IV. Functionalized Carbocylic Compounds via Organometallic Methods	555	(3)
V. Experimental Procedures	558	(7)
References and Notes	565	(4)
26. The Conversion of Carbohydrates to Cyclohexane Derivatives	569	(24)
Robert J. Ferrier
I. Introduction	570	(1)
II. Methods	571	(14)
III. Experimental Procedures	585	(5)
References	590	(3)
PART VII TOTAL SYNTHESIS OF SUGARS FROM NONSUGARS	593	(44)
Stephen Hanessian
27. Total Synthesis of Amino Sugars	595	(20)
Janusz Jurczak
I. Introduction	595	(1)
II. Methods	596	(5)
III. Experimental Procedures	601	(10)
References	611	(4)
28. Total Synthesis of Sugars	615	(22)
Aleksander Zamojski
I. Introduction	615	(2)
II. Methods	617	(5)
III. Experimental Procedures	622	(12)
References and Notes	634	(3)
Index	637