Cyanohydrins, Fischer cyanohydrin synthesis

C. S. Hudson, The Fischer Cyanohydrin Synthesis and the Configurations of Higher-carbon Sugars and... 

Lemieux and Spohr (Alberta) here trace our understanding of enzyme specificity in broad perspective as they assess Emil Fischer s lock and key concept advanced a century ago in relation to current ideas of molecular recognition. It may be noted that the very first article in Volume 1 of Advances, by Claude S. Hudson, was devoted to the Fischer cyanohydrin synthesis and the consequences of asymmetric induction. 

The free nitriles of iV-methyl-L-glucosaminic acid and iV-methyl-L-mannosaminic acid have been prepared by Wolfrom, Thompson and Hooper by the Kiliani-Fischer cyanohydrin synthesis. 

Among the classic methods for the extension of the aldose chain by one carbon atom from the reducing end [9J, the Kiliani-Fischer cyanohydrin synthesis [10] is a milestone in carbohydrate chemistry. However after 110 years from discovery and numerous applications [11], including the preparation of carbon and hydrogen isotopically labeled compounds for mechanistic and structural studies [12], there are still several drawbacks that make the method impractical. These are the low and variable degree of selectivity and the harsh reaction conditions that are required to reveal the aldose from either the aldonic acid or directly from the cyanohydrin. Synthetic applications that have appeared in recent times confirmed these limitations. For instance, a quite low selectivity was registered [13] in the addition of the cyanide ion to the D-ga/acfo-hexodialdo-l,5-pyranose derivative 1... 

How, M. J., Brimacombe, J. S., and Stacey, M., The Pneumococcal Polysaccharides, 19, 303-357 Hudson, C. S., Apiose and the Glycosides of the Parsley Plant, 4, 57-74 Hudson, C. S., The Fischer Cyanohydrin Synthesis and the Configurations of Higher-carbon Sugars and Alcohols,... 

The synthesis of D-psicose as a colorless sirup ([< ]% + 3.1° in water) by Steiger and Reichstein13 may be regarded as the first authentic preparation of this ketohexose. The Kiliani-Fischer cyanohydrin synthesis furnished D-allonic lactone (VII) from D-ribose. This lactone, on reduction with sodium amalgam, gave D-allose (VIII) which was transformed into D-psicose (I) by refluxing with pyridine. Pyridine had been introduced into the Lobry de Bruyn-Van Ekenstein reaction by Fischer, Danilov and their coworkers.13 ... 

Film, cellulose acetate, I, 300 cellulose ester, I, 325 starch acetate, I, 297 Fischer cyanohydrin synthesis of higher-C sugars, I, 1-38... 

THE FISCHER CYANOHYDRIN SYNTHESIS AND THE CONFIGURATIONS OF HIGHER-CARBON SUGARS AND ALCOHOLS... 

XL Improvements in the Details of the Fischer Cyanohydrin Synthesis of Higher-... 

It will be noticed that the future application of the Fischer cyanohydrin synthesis to n-altrose should lead to two heptitols, one of which (n-altro-D- luco-heptitol) should be the enantiomorph of the known D-gulo-L-talo-heptitol, while the other (o-altro-D-manno-heptitol) should be identical with natural volemitol (D-manno-D-[Pg.12]

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