Organic Synthesis With Carbohydrates

by Boons, Geert-Jan; Hale, Karl J.

• ISBN13: 9780632045082
• ISBN10: 0632045086
• Format: Hardcover
• Copyright: 2000-06-01
• Publisher: John Wiley & Sons Inc

Table of Contents

PART A: STRUCTURE AND SYNTHESIS OF SACCHARIDES AND GLYCOPROTEINS
Mono- and oligosaccharides: structure, configuration and conformation	1	(25)
Introduction	1	(1)
Configuration of monosaccharides	2	(5)
Conformational properties of monosaccharides	7	(11)
Ring shapes of pyranoses and furanoses	7	(3)
The anomeric effect	10	(5)
The equilibrium composition of monosaccharides in solution	15	(3)
Conformational properties of oligosaccharides	18	(1)
Acid-catalysed glycoside bond formation and cleavage	19	(7)
References	24	(2)
Protecting groups	26	(30)
Introduction	26	(1)
Ether protecting groups	27	(14)
Benzyl ethers	27	(6)
p-Methoxybenzyl ethers	33	(1)
Allyl ethers	34	(3)
Triphenylmethyl ethers	37	(1)
Silyl ethers	38	(3)
Acetal protecting groups	41	(5)
Benzylidene acetals	41	(2)
Isopropylidene acetals	43	(2)
Dispirodiketal and cyclohexane-1,2-diacetal groups	45	(1)
Ester protecting groups	46	(3)
Anomeric protecting groups	49	(2)
Amino protecting groups	51	(5)
Phthalimides	52	(1)
Azides	52	(1)
References	53	(3)
Functionalised saccharides	56	(47)
General introduction	56	(1)
Deoxyhalogeno sugars	56	(9)
Introduction	56	(1)
Direct halogenation of alcohols	56	(4)
Displacement reactions	60	(3)
Miscellaneous methods	63	(2)
Unsaturated sugar derivatives	65	(6)
Introduction	65	(1)
Glycals	66	(3)
Isolated double bonds	69	(1)
6-Deoxy-hex-5-enopyranose derivatives	69	(2)
Deoxy sugars	71	(5)
Introduction	71	(1)
Reduction of halides, sulfonates and epoxides	72	(2)
Radical deoxygenation of thiocarbonyl derivatives	74	(2)
Amino sugars	76	(8)
Introduction	76	(1)
The preparation of amino sugars by nucleophilic displacement	77	(4)
Addition to glycals	81	(1)
Reduction of oximes	82	(2)
Intramolecular substitutions	84	(1)
Epoxy sugars	84	(3)
Sulfated saccharides	87	(2)
Introduction	87	(2)
O and N sulfation	89	(1)
Phosphorylated saccharides	89	(14)
Introduction	89	(1)
Non-anomeric sugar phosphates	90	(4)
Anomeric phosphates	94	(2)
References	96	(7)
Oligosaccharide synthesis	103	(52)
Introduction	103	(1)
Chemical glycosidic bond synthesis	103	(7)
Glycosyl halides	105	(2)
Trichloroacetimidates	107	(2)
Thioglycosides	109	(1)
Stereoselective control in glycosidic bond synthesis	110	(12)
Neighbouring-group-assisted procedures	111	(1)
In situ anomerisation	112	(2)
Glycosylation with inversion of configuration	114	(4)
Solvent participation	118	(2)
Intramolecular aglycon delivery	120	(2)
Preparation of 2-amino-2-deoxy-glycosides	122	(2)
Formation of glycosides of N-acetyl-neuraminic acid	124	(3)
The introduction of 2-deoxy glycosidic linkages	127	(4)
Convergent block synthesis of complex oligosaccharides	131	(4)
Chemoselective glycosylations and one-pot multistep glycosylations	135	(4)
Solid-phase oligosaccharide synthesis	139	(5)
Enzymatic glycosylation strategies	144	(11)
Glycosyl transferases	146	(2)
Glycosyl hydrolases	148	(2)
References	150	(5)
The chemistry of O- and N-linked glycopeptides	155	(20)
Introduction	155	(1)
Strategies for the chemical synthesis of glycopeptides	156	(4)
Protecting groups in glycopeptide synthesis	160	(1)
Chemical synthesis of serine O-glycoside derivatives	161	(5)
The synthesis of N-glycopeptides	166	(1)
Solution-phase and solid-phase glycopeptide synthesis	167	(4)
Enzyme-mediated glycopeptide synthesis	171	(4)
References	172	(3)
PART B: NATURAL PRODUCT SYNTHESIS FROM MONOSACCHARIDES
(-)-Echinosporin	175	(11)
Introduction	175	(1)
Smith's retrosynthetic analysis of (-)-echinosporin	175	(1)
Smith's (-)-echinosporin synthesis	176	(5)
Mechanistic analysis of some key reactions employed in the Smith (-)-echinosporin synthesis	181	(5)
References	184	(2)
(+)-Zaragozic acid C	186	(14)
Introduction	186	(1)
Carreira's retrosynthetic analysis of (+)-zaragozic acid C	186	(2)
Carreira's total synthesis of (+)-zaragozic acid C	188	(6)
Mechanistic analysis of some of the key steps in Carreira's synthesis of (+)-zaragozic acid C	194	(6)
References	198	(2)
(+)-Neocarzinostatin	200	(17)
Introduction	200	(1)
Myers' retrosynthetic planning for the synthesis of (+)-neocarzinostatin	200	(6)
Myers' total synthesis of (+)-neocarzinostatin	206	(5)
Mechanistic analysis of the key steps in Myers'(+)-neocarzinostatin synthesis	211	(6)
References	215	(2)
(+)-Castanospermine	217	(7)
Introduction	217	(1)
The Pandit retrosynthetic analysis of (+)-castanospermin	217	(1)
Pandit's total synthesis of (+)-castanospermine	218	(3)
Mechanistic analysis of the Pandit synthesis of (+)-castanospermine	221	(3)
References	222	(2)
(-)-Silphiperfolene	224	(10)
Introduction	224	(1)
The Fraser-Reid retrosynthetic analysis of (-)-silphiperfolene	224	(5)
Fraser-Reid's total synthesis of (-)-silphiperfolene	229	(3)
Mechanistic analysis of the Fraser-Reid (-)-silphiperfolene synthesis	232	(2)
References	232	(2)
(-)-Allosamizoline	234	(13)
Introduction	234	(1)
The Kuzuhara retrosynthetic analysis of (-)-allosamizoline	235	(1)
The Kuzuhara total synthesis of (-)-allosamizoline	236	(3)
Mechanistic analysis of the Kuzuhara (-)-allosamizoline synthesis	239	(1)
Simpkins' retrosynthetic strategy for (-)-allosamizoline	239	(2)
Simpkins' total synthesis of (-)-allosamizoline	241	(2)
Mechanistic analysis of some key steps in the Simpkins (-)-allosamizoline synthesis	243	(2)
Epilogue	245	(2)
References	245	(2)
(-)-Reiswigin A	247	(12)
Introduction	247	(1)
The Kim retrosynthetic analysis of (-)-reiswigin A	247	(4)
The Kim total synthesis of (-)-reiswigin A	251	(3)
Mechanistic points of interest in the (-)-reiswigin A synthesis	254	(5)
References	257	(2)
(-)-Octalactin A	259	(11)
Introduction	259	(1)
The Buszek retrosynthetic analysis of (-)-octalactin A	259	(5)
Buszek's total synthesis of (-)octalactin A	264	(1)
Items of mechanistic interest in the Buszek (-)-octalactin A synthesis	265	(5)
References	269	(1)
(-)-ACRL toxin I	270	(10)
Introduction	270	(1)
The Lichtenhaler retrosynthetic analysis of (-)-ACRL toxin I	270	(3)
Lichtenhaler's total synthesis of the (-)-ACRL toxin I	273	(4)
Items of mechanistic interest in the Lichtenhaler synthesis of the (-)-ACRL toxin I	277	(2)
Epilogue	279	(1)
References	279	(1)
(+)-Gabosine E	280	(6)
Introduction	280	(1)
The Lygo retrosynthetic analysis of (+)-gabosine E	280	(2)
The Lygo synthesis of (+)-gabosine E	282	(2)
Points of mechanistic interest in the Lygo (+)-gabosine E synthesis	284	(2)
References	285	(1)
(-)-Augustamine and (-)-amabiline	286	(6)
Introduction	286	(1)
The Pearson retrosynthetic analysis of (-)-augustamine	286	(2)
The Pearson total synthesis of (-)-augustamine	288	(2)
Pearson's synthesis of (-)-amabiline	290	(1)
Mechanistic analysis of the (-)-augustamine and (-)-amabiline syntheses	290	(2)
References	291	(1)
(-)-FK506	292	(37)
Introduction	292	(1)
The Danishefsky retrosynthetic analysis of (-)-FK506	292	(3)
The Danishefsky formal total synthesis of (-)-FK506	295	(7)
The Merck endgame used in the first total synthesis of (-)-FK506	302	(3)
Smith's retrosynthetic analysis of (-)-FK506	305	(3)
The Smith formal total synthesis of (-)-FK506	308	(9)
Items of interest in the Danishefsky and Smith total syntheses of (-)-FK506	317	(12)
References	326	(3)
(3S,5S)-5-Hydroxypiperazic acid	329	(5)
Introduction	329	(1)
The Hale retrosynthetic analysis of (3S,5S)-5-hydroxypiperazic acid	329	(2)
The Hale total synthesis of (3S,5S)-5-hydroxypiperazic acid	331	(1)
Points of mechanistic interest in the Hale (3S,5S)-5-hydroxypiperazic acid synthesis	332	(2)
References	333	(1)
Index	334