2001
DOI: 10.1021/jo0057452
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Fragmentation of Carbohydrate Anomeric Alkoxy Radicals. Synthesis of Polyhydroxy Piperidines and Pyrrolidines Related to Carbohydrates

Abstract: Imino sugars of the piperidine and pyrrolidine types can be specifically obtained when protected 5-amino-5-deoxyfuranopentoses, 5-amino-5-deoxyfuranohexoses, 6-amino-6-deoxyfuranohexoses, and 6-amino-6-deoxypyranohexoses undergo a tandem alkoxy radical beta-fragmentation-intramolecular cyclization reaction. The reaction is promoted by the system: iodosylbenzene-iodine under mild conditions. The tert-butoxycarbonyl, benzyloxycarbonyl, and diphenylphosphinoyl radicals have been studied as amino-protecting groups… Show more

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Cited by 54 publications
(29 citation statements)
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“…Next, we turned to synthesis of CPU analogs modified at the C5 0 position of the cyclopentenyl moiety ( Figure 2B). Selective deprotection of TBDPS with tetra-n-butylammonium fluoride revealed the primary hydroxyl group (Song et al, 2001), which was then methylated in the presence of Ag 2 O (Francisco et al, 2001) to afford the protected 5 0 -methoxy-CPU. Alternatively, the alcohol could be converted to a terminal fluoride with diethylamino sulfurotrifluoride (Moon et al, 2004), resulting in protected 5 0 -fluoro CPU.…”
Section: Diversity-oriented Syntheses Of Cpu Analogsmentioning
confidence: 99%
“…Next, we turned to synthesis of CPU analogs modified at the C5 0 position of the cyclopentenyl moiety ( Figure 2B). Selective deprotection of TBDPS with tetra-n-butylammonium fluoride revealed the primary hydroxyl group (Song et al, 2001), which was then methylated in the presence of Ag 2 O (Francisco et al, 2001) to afford the protected 5 0 -methoxy-CPU. Alternatively, the alcohol could be converted to a terminal fluoride with diethylamino sulfurotrifluoride (Moon et al, 2004), resulting in protected 5 0 -fluoro CPU.…”
Section: Diversity-oriented Syntheses Of Cpu Analogsmentioning
confidence: 99%
“…For example, Havare and Plattner reported the oxidative cleavage of α-aryl aldehydes using iodosylbenzene to give chain-shortened carbonyl compounds and formaldehyde [ 71 ]. In the field of carbohydrate chemistry, similar deformylation by action of hypervalent iodine has also been demonstrated: the β-fragmentation reaction of an anomeric alkoxy radical of carbohydrates was mediated by a hypervalent iodine reagent [ 73 ]. The reaction results in the formation of carbohydrates with a reduction of one carbon.…”
Section: Reviewmentioning
confidence: 99%
“…This method has been applied to prepare chiral pyrrolidine 127 from carbohydrate 126 by the trapping of cationic intermediates with internal nitrogen nucleophiles (Scheme 39). 153 Photochemical generation of an anomeric alkoxyl radical from protected glucofuranose-derived bromohydrine 128 [PhI(OAc) 2 /I 2 ] leads to 1-bromo-1-iodo pentose-derivative 129 (Scheme 39) which serves as valuable building block since it can be reacted with aldehydes in the pres-ence of chromium dichloride to afford chain-elongated olefins (not shown in Scheme 39). 154 Scheme 39 Synthesis of chiral pyrrolidine 127 from carbohydratederived lactol 126 (top) 153 and application of a regioselective alkoxyl radical fragmentation in the synthesis of 1,1-dihalogen-substituted building block 129 (bottom).…”
Section: Scheme 38mentioning
confidence: 99%