Tw. Stringfield et Re. Shepherd, Formation of a W(CO)(5)-furanosylidene complex from ribose without the useof protective groups, INORG CHIM, 325(1-2), 2001, pp. 51-57
[W(CO)(5)(acetone)], formed by photolysis of W(CO)(6), undergoes a spontane
ous reaction at the C-1 position Of D-ribose in d(6)-acetone in 24 h in qua
ntitative yield to form water and the W(CO)(5)-furanosylidene complex, exhi
biting a characteristic carbene C-13 resonance at 427 ppm. The reaction pro
ceeds without protection of any of the ribose hydroxyl groups, and occurs o
nly at the C-1 position. The same reaction does not occur for fructose, D()-ribonic gamma -lactone, or 2-deoxy-D-ribose. No reaction occurred with th
e pyranose sugars, D-glucose or D-galactose. A pathway via oxidative additi
on to C-H of the open chain aldehyde form of ribose is proposed. Insertion
of W(CO), into the C-H bond, followed by rearrangement of the W(II)(CO)(5)-
acyl hydride to a hydroxy carbene that recyclizes to the coordinated furano
sylidene accounts for the reactivity Of D-ribose and the absence of reactiv
ity for the other sugars. Molecular mechanics calculations were carried out
using SPARTAN and MMFF94 programs for the free sugars D-ribose and D-gluco
se and their C-1-coordinated carbenes of W(CO), The carbene complexes are e
nergetically uphill of the free sugars by 54.8 and 63.3 kcal mol (-1) for r
ibose and glucose, respectively. Therefore, elimination of water is a key f
actor in the net driving force to form the coordinated carbene Of D-ribose.
The structures reveal a useful planarity at C-1 which places the filled p-
orbital on the O atom alpha to the carbene in the proper perpendicular arra
ngement to maximize resonance with the carbene carbon. The theoretical stru
cture for the D-glucose analogue adopts sufficient puckering of the chair a
rrangement of the glucose to cause a misalignment of the alpha O p-orbital,
which would decrease the inherent stablity, consistent with the absence of
forming such a species. (C) 2001 Elsevier Science B.V. All rights reserved
.