Synthesis of fused cyclic systems containing medium-sized rings through tandem ROM-RCM of norbornene derivatives embedded in a carbohydrate template

A general approach for the synthesis of fused cyclic systems containing medium-sized rings (7-9) has been developed. The key steps involve a diastereoface-selective Diels-Alder reaction of the dienophiles 4a-d attached to a furanosugar with cyclopentadiene and ring opening (ROM)-ring closing metathesis (RCM) of the resulting norbornene derivatives 10a-d and 11a-d. Diels-Alder reaction of the dienophiles 4a-d with cyclopentadiene in the absence of a catalyst produced 10a-d as the major product arising through addition of the diene to the unhindered Si-face. The most interesting and new aspect of the Diels-Alder reaction of these dienophiles is the accessibility of the Re-face that was blocked by the alkenyl chains under Lewis acid catalysis producing the diastereoisomers 11a-d exclusively. The reversal of facial selectivity from an uncatalyzed reaction to a catalyzed one is unprecedented. The observed stereochemical dichotomy is attributed to rotation of the enone moiety along the or bond linking the sugar moiety during formation of the chelate 13. This makes the Re-face of the enone moiety in 4a-d unhindered. Diels-Alder reaction of the carbocyclic analogue 15 under Lewis acid catalysis produced a 1: 1 mixture of the adducts 16 and 17 confirming the participation of sugar ring oxygen in chelate formation. Finally ROM-RCM of 10a-d and 11a-d with Grubbs' catalyst afforded the cis-syn-cis and cis-anti-cis bicyclo-annulated sugars 21a-d and 23a-d, respectively, containing 7-9 membered rings.

Quality time [QoS in 802.11e]

Wireless local area networks (WLANs) based on the IEEE 802.11 standard are now widespread. Most are used to provide access for mobile devices to a conventional wired infrastructure, and some are used where wires are not possible, forming an ad hoc network of their own. There are several varieties at the physical or radio layer (802.11, 802.11a, 802.11b, 802.11g), with each featuring different data rates, modulation schemes and transmission frequencies. However, all of them share a common medium access control (MAC) layer. As this is largely based on a contention approach, it does not allow prioritising of traffic or stations, so it cannot easily provide the quality of service (QoS) required by time-sensitive applications, such as voice or video transmission. In order to address this shortfall of the technology, the IEEE set up a task group that is aiming to enhance the MAC layer protocol so that it can provide QoS. The latest draft at the time of writing is Draft 11, dated October 2004. The article describes the yet-to-be-ratified 802.11e standard and is based on that draft.