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. 2006 Oct 26;8(22):5149-52.
doi: 10.1021/ol062076r.

De novo asymmetric syntheses of SL0101 and its analogues via a palladium-catalyzed glycosylation

Mingde Shan  1 , George A O'Doherty
Affiliations

De novo asymmetric syntheses of SL0101 and its analogues via a palladium-catalyzed glycosylation

Mingde Shan et al. Org Lett. .

Abstract

The enantioselective syntheses of naturally occurring kaempferol glycoside SL0101 (1a) and its analogues 1b-e, as well as their enantiomers, have been achieved in 7-10 steps. The routes rely upon a diastereoselective palladium-catalyzed glycosylation, ketone reduction, and dihydroxylation to introduce the rhamno-stereochemistry. The asymmetry of the sugar moiety of these kaempferol glycosides was derived from Noyori reduction of an acylfuran. An acetyl group shift from an axial (C-2) to equatorial position (C-3) under basic conditions was also described. [reaction: see text]

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Figures

Figure 1
Figure 1
Kaempferol glycoside SL0101 (1a) and its analogues (1b-e), and their Rsk2 inhibitory activities.
Scheme 1
Scheme 1
Retrosynthetic analysis of kaempferol rhamnosides (1a-e)
Scheme 2
Scheme 2
Synthesis of kaempferol-3-α-L-rhamnoside (1b).
Scheme 3
Scheme 3
Synthesis of kaempferol-3-α-L-2″,3″,4″-O-triacetylrhamnoside (1c).
Scheme 4
Scheme 4
Synthesis of kaempferol-3-α-L -4″-O-acetylrhamnosid(1d).
Scheme 5
Scheme 5
Synthesis of kaempferol-3-α-L-2″,4″-O-diacetylrhamnoside (1e).
Scheme 6
Scheme 6
Synthesis of SL0101 (1a)
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