Novel Concise Synthesis of (±)-Noviose and l-(+)-Noviose by Palladium-Catalyzed Epoxide Opening

Abstract

We established a novel, concise synthetic route for obtaining noviose, the deoxy sugar component of aminocoumarin antibiotics. l-(+)-Noviose was successfully synthesized by utilizing a palladium-catalyzed epoxide-opening reaction and the subsequent lactone formation as key reactions, starting from a nonsugar chiral epoxide, which is easily available in both enantiomeric forms.

Key words

noviose - novobiocin - aminocoumarin antibiotics - palladium-catalyzed epoxide opening

References

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  (-)-7b: [α]_D ^²6.9 -33.2 (c 1.05, CHCl₃) {Lit.^¹6 [α]_D ^²0 -30.64 (c 1.155, CHCl₃)}; IR (neat): 2954, 1724, 1657, 1437, 1379, 1319, 1296, 1263, 1173, 980, 804 cm^-¹; ^¹H NMR (270 MHz, CDCl₃): δ = 6.84 (dd, J = 6.5, 15.7 Hz, 1 H), 6.12 (dd, J = 1.1, 15.6 Hz, 1 H), 3.76 (s, 3 H), 3.33 (dd, J = 0.9, 6.4 Hz, 1 H), 1.41 (s, 3 H), 1.29 (s, 3 H); ^¹³C NMR (67.8 MHz, CDCl₃): δ = 166.1, 143.1, 124.4, 62.1, 61.7, 51.7, 24.6, 18.6

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  See also: ref. 19

• 17c

  8: IR (neat): 2981, 2933, 1711, 1639, 1612, 1446, 1367, 1308, 1277, 1213, 1161, 1140, 1039, 991, 879 cm^-¹; ^¹H NMR (270 MHz, CDCl₃): δ = 7.56 (dd, J = 11.5, 15.2 Hz, 1 H), 5.99 (br dq, J = 1.1, 11.7 Hz, 1 H), 5.76 (d, J = 15.2 Hz, 1 H), 4.20 (q, J = 7.1 Hz, 2 H), 1.89 (d, J = 0.9 Hz, 3 H), 1.88 (s, 3 H), 1.30 (t, J = 7.1 Hz, 3 H); ^¹³C NMR (67.8 MHz, CDCl₃): δ = 167.7, 146.2, 141.0, 123.7, 118.6, 60.1, 26.5, 18.9, 14.3

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  This article was occasionally quoted as the reference for the synthesis of (±)-noviose by mistake, which, however, certainly includes ^¹H NMR data of synthesized methyl dl-novioside along with those of naturally derived noviose.

20

Acid-catalyzed epoxide opening of (±)-7a (cat. H₂SO₄-MeOH or BF₃˙OEt₂-MeOH) resulted in a ratio of approximately 1:4 to 1:6 (desired/undesired), which was roughly estimated by ^¹H NMR analysis of the crude products.