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DOI: 10.1055/s-0029-1216835
Rhodium Carbenoid Induced [1,2]-Migration in an l-Lyxo-Configured α-Diazo β-Keto Ester: Synthesis of a New Griseolic Acid Analogue
Publication History
Publication Date:
19 May 2009 (online)
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Abstract
An appropriately substituted α-diazo β-keto ester, prepared from d-glucose, on treatment with a catalytic amount of dirhodium tetraacetate gave a strained 1,5-dioxabicyclo[3.3.0]octane ring system with concomitant diastereoselective formation of a quaternary carbon substituted with both an ethoxycarbonyl group and a 2-ethoxy-2-oxoethyl group; the product is a key intermediate in the synthesis of a new griseolic acid analogue.
Key words
carbenoids - carbohydrates - carboxylic acids - diazo compounds - oxygen heterocycles
- Supporting Information for this article is available online:
- Supporting Information
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References
Selective hydrolysis of the 5,6-O-isopropylidene group in 3c was possible probably because of the α-orientation of the 5,6-diol in the furanose ring; transfer of a proton from the protonated oxygen at the C-6 carbon to the C-1 acetonide facilitates the 1,2-acetonide deprotection competitively. Attempts with various other acidic reagents, such as 10% H2SO4, CuCl2˙2H2O, 30% HClO4, or acidic resin (Indion 140), failed to give good yields.
13The unstable nature of compound 7 precluded further characterization. At this stage, attempts were made to convert the keto compound 7 into one with an olefinic functionality at the ring junction. Thus, attempts at the reaction of 7 by using the Shapiro protocol (SO2Cl2 and POCl3) led to a complex mixture. Attempts to activate the hydroxyl functionality by using mesyl chloride and subsequent treatment with base under reflux were also unsuccessful.
14Our attempts to isolate the other diastereomer (C-5β-OH) in a pure form were unsuccessful.
15In the ¹H NMR
spectrum of 9, the C-5 appeared at δ = 5.
5 as a doublet (J
5,4 = 5.00
Hz). In 1D NOSEY irradiation, one of the C-7 methylene protons at δ = 2.48
showed a NOE with H-3, H-4, H-5, indicating a syn-relationship
between the
-CCH2COOEt group and the
sugar ring protons, and confirming our earlier assignment.
The ¹H NMR spectrum of 10 shows the presence of an anomeric mixture in the ratio 1:15 in favor of the β-anomer.