Metathesis‐Based De Novo Synthesis of Noviose

Abstract

The rare carbohydrate L‐(+)‐noviose was synthesized from enantiomerically pure L‐lactate. The configuration at C‐4 was established by diastereoselective nucleophilic addition to an in‐situ‐generated lactaldehyde. The resulting homoallylic alcohol was further transformed into a set of ring‐closing metathesis (RCM) precursors. These compounds were converted into noviose in few steps using RCM and RCM–allylic‐oxidation sequences.

Recent applications in natural product synthesis of dihydrofuran and -pyran formation by ring-closing alkene metathesis

“…The second synthesis of L-(+)-noviose (79) uses diastereoselective (90 : 10 dr) vinylation of a lactic acid-derived aldehyde to introduce the methoxy-bearing stereocentre (Scheme 22). 35 RCM with GI is followed by addition of t-BuOOH and conversion to a pyranone 80 in a one-pot procedure; the hydroperoxide converts GI into a catalyst for allylic oxidation. Subsequent MOM deprotection and methylation intersects with the earlier synthesis.…”

De Novo Synthesis of Mono‐ and Oligosaccharides via Dihydropyran Intermediates

“…[49] Ar ecent example of the de novo synthesis of l-noviose is shown in Scheme 19. [50] Many other groups also used similar strategies for the de novo synthesis of rare sugarsa nd their analogues. [51] For example, the group of Wang systematically prepared as eries of 2,6-dideoxy-sugars by using the RCM strategy.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…265) [686], synrotolide (e.g. 266) [687,688], coibacins A and B [689], boronolide, anamarine and epi-spicegerolide [690], noviose (and an alternative route based on sixmembered ring allylic ether-forming RCM followed by allylic oxidation) [691], an intermediate for brevipolide…”