Thieme Chemistry Journal Awardees - Where
are They Now? Synthesis of the Marine Glycolipid Dioctadecanoyl
Discoside

Gordon J. Florence; Tashfeen Aslam; Gavin J. Miller; Gavin D. S. Milne; Stuart J. Conway

doi:10.1055/s-0029-1218301

LETTER

Thieme Chemistry Journal Awardees - Where are They Now? Synthesis of the Marine Glycolipid Dioctadecanoyl Discoside

Gordon J. Florence*^a, Tashfeen Aslam^a, Gavin J. Miller^a, Gavin D. S. Milne^a, Stuart J. Conway*^b
^a Centre for Biomolecular Sciences, School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK
Fax: +44(1334)463808; e-Mail: gjf1@st-andrews.ac.uk;
^b Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK
Fax: +44(1865)285002; e-Mail: stuart.conway@chem.ox.ac.uk;

Abstract

All articles of this category

Abstract

The first synthesis of the inositol-containing marine glycolipid dioctadecanoyl discoside is reported. The key glycosylation reaction proceeds with β-selectivity at reduced temperature. The separable anomers could be readily progressed to afford discoside, its peracetate and the unnatural β-derivatives.

Key words

marine sponge - glycolipid - mannose - glycosylation - inositol

Full Text

References

References and Notes

<A NAME="RS09409ST-1A">1a</A> Udenfriend S. Kodukula K. Ann. Rev. Biochem. 1995, 64: 563

<A NAME="RS09409ST-1B">1b</A> McConville MJ. Ferguson MAJ. Biochem. J. 1993, 294: 305

<A NAME="RS09409ST-2A">2a</A> Briken V. Porcelli SA. Besra GS. Kremer L. Mol. Microbiol. 2004, 53: 391

<A NAME="RS09409ST-2B">2b</A> Gilleron M. Nigou J. Cahuzac B. Puzo G. J. Mol. Biol. 1999, 285: 2147

<A NAME="RS09409ST-3A">3a</A> van den Boogaard J. Kibiki GS. Kisanga ER. Boeree MJ. Aarnouste RE. Antimicrob. Agents Chemother. 2009, 53: 849

<A NAME="RS09409ST-3B">3b</A> Sharma SK. Mohan A. Chest 2006, 130: 261

<A NAME="RS09409ST-4A">4a</A> Boonyarattanakalin S. Liu X. Michieletti M. Lepenies B. Seeberger PH. J. Am. Chem. Soc. 2008, 130: 16791

<A NAME="RS09409ST-4B">4b</A> Gilleron M. Quesniaux VF. Puzo G. J. Biol. Chem. 2003, 278: 29880

<A NAME="RS09409ST-5A">5a</A> Ainge GD. Parlane NA. Denis M. Dyer BS. Härer A. Hayman CM. Larsen DS. Painter GF. J. Org. Chem. 2007, 72: 5291

<A NAME="RS09409ST-5B">5b</A> Ainge GD. Hudson J. Larsen DS. Painter GF. Gill GS. Harper JL. Bioorg. Med. Chem. 2006, 14: 5632

<A NAME="RS09409ST-6">6</A> Smith A. Nobmann P. Henehan G. Bourke P. Dunne J. Carbohydr. Res. 2008, 343: 2557

<A NAME="RS09409ST-7">7</A> Barbieri L. Costantino V. Fattorusso E. Mangoni A.
J. Nat. Prod. 2005, 68: 1527

<A NAME="RS09409ST-8">8</A> Prottey C. Ballou CE. J. Biol. Chem. 1968, 243: 6196

<A NAME="RS09409ST-9A">9a</A> Keddie NS. Bultynck G. Luyten T. Slawin AMZ. Conway SJ. Tetrahedron: Asymmetry 2009, 20: 857

<A NAME="RS09409ST-9B">9b</A> Bello D. Aslam T. Bultynck G. Slawin AMZ. Roderick HL. Bootman MD. Conway SJ. J. Org. Chem. 2007, 72: 5647

<A NAME="RS09409ST-9C">9c</A> Conway SJ. Thuring JW. Andreu S. Kvinlaug BT. Roderick HL. Bootman MD. Holmes AB. Aust. J. Chem. 2006, 59: 887

<A NAME="RS09409ST-9D">9d</A> For a review, see: Conway SJ. Miller GJ. Nat. Prod. Rep. 2007, 24: 687

<A NAME="RS09409ST-10A">10a</A> Lee HW. Kishi Y. J. Org. Chem. 1985, 50: 4402

<A NAME="RS09409ST-10B">10b</A> For a review, see: Sureshan KM. Shashidhar MS. Praveen T. Das T. Chem. Rev. 2003, 103: 4477

<A NAME="RS09409ST-11">11</A> Billington DC. Baker R. Kulagowski JJ. Mawer IM. Vacca JP. Desolms SJ. Huff JR. J. Chem. Soc., Perkin Trans. 1 1989, 1423

<A NAME="RS09409ST-12">12</A> Painter GF. Grove SJA. Gilbert IH. Holmes AB. Raithby PR. Hill ML. Hawkins PT. Stephens LR. J. Chem. Soc., Perkin Trans. 1 1999, 1423

<A NAME="RS09409ST-13">13</A> Boons GJ. Burton A. Isles S. Chem. Commun. 1996, 141

<A NAME="RS09409ST-14A">14a</A> Crich D. Sun S. Tetrahedron 1998, 54: 8321

<A NAME="RS09409ST-14B">14b</A> Kartha KPR. Field RA. Tetrahedron 1997, 53: 11753

<A NAME="RS09409ST-15">15</A> Nieses B. Steglich W. Angew. Chem. Int. Ed. Engl. 1978, 17: 522

<A NAME="RS09409ST-16A">16a</A> Zuurmond HM. van der Laan SC. van der Marel GA. van Boom JH. Carbohydr. Res. 1991, 215: C1

<A NAME="RS09409ST-16B">16b</A> Veeneman GH. van Leeuwen SH. van Boom JH. Tetrahedron Lett. 1990, 31: 1331

<A NAME="RS09409ST-16C">16c</A> Binder WH. Kahlig H. Schmidt W. Tetrahedron 1994, 50: 10407

<A NAME="RS09409ST-17A">17a</A> Crich D. Sun S. J. Am. Chem. Soc. 1997, 119: 11217

<A NAME="RS09409ST-17B">17b</A> Marsh SJ. Ravindranathan KP. Field RA. Synlett 2003, 1376

<A NAME="RS09409ST-18A">18a</A> Ainge GD. Parlane NA. Denis M. Hayman CM. Larsen DS. Painter GF. Bioorg. Med. Chem. 2006, 14: 7615

<A NAME="RS09409ST-18B">18b</A> Uriel C. G ómez AM. López JC. Fraser-Reid B. Eur. J. Org. Chem. 2009, 403

The ^¹H NMR of 3 in 1% CD₃OD/CDCl₃ gave a broad, unresolved spectrum. Selected data for 3: Amorphous colourless solid; mp 110-115 ˚C; ^¹H NMR (400 MHz, 1% CD₃OD/CDCl₃): δ = 5.40-4.90 (m, 4 H), 4.50-3.30 (m, 8 H), 2.40-2.10 (m, 4 H, H-2′′ and H-2′′′), 1.65-1.40 (m, 4 H, H-3′′ and H-3′′′), 1.20 (s, 56 H, 28 × CH₂-lipid), 0.85-0.75 (m, 6 H, H-18′′ and H-18′′′); LRMS (MALDI-TOF):
m/z (%) = 897.9 (20) [M + Na]⁺, 453.5 (100).

Data for α-peracetate 14: Oil; R _f = 0.46 (PE-EtOAc, 6:4); [α]_D ^²0 +11.3 (c 0.73 CHCl₃) (Lit.^³ +12.0, c 0.5 CHCl₃); IR (neat): 2918.2, 2850.3, 1753.2, 1369.3, 1225.2, 1043.9 cm^-¹; ^¹³C NMR (400 MHz, CDCl₃): δ = 5.53 (dd, J = 10.3, 10.2 Hz, 1 H, H-4), 5.50 (dd, J = 10.4, 9.6 Hz, 1 H, H-6), 5.43-5.40 (m, 2 H, H-3′ and H-4′), 5.38-5.36 (m, 1 H, H-2′), 5.19 (t, J = 9.6 Hz, 1 H, H-5), 5.09 (dd, J = 10.4, 2.4 Hz, 1 H, H-3), 5.00 (dd, J = 10.8, 2.8 Hz, 1 H, H-1), 4.95 (d, J = 1.6 Hz, 1 H, H-1′), 4.30 (t, J = 2.8 Hz, 1 H, H-2), 4.26 (dd, J = 12.3, 4.2 Hz, 1 H, H-6′a), 4.20-4.15 (m, 1 H, H-5′), 4.09 (dd, J = 12.3, 2.4 Hz, 1 H, H-6′b), 2.36-2.27 (m, 4 H, H-2′′ and H-2′′′), 2.14 (s, 3 H), 2.09 (s, 3 H), 2.07 (s, 3 H), 2.03 (s, 3 H), 2.02 (s, 3 H), 2.01 (s, 3 H), 2.00 (s, 3 H), 1.65-1.56 (m, 4 H, H-3′′ and H-3′′′), 1.33-1.22 (m, 56 H, 28 × CH₂-lipid), 0.89-0.83 (m, 6 H, H-18′′ and H-18′′′); ^¹³C NMR (101 MHz, CDCl₃): δ = 173.4, 172.5, 169.84, 169.78, 169.76, 169.6, 169.5, 169.4, 169.3, 99.5, 76.4, 70.6, 70.4, 69.6 (3 × C), 69.5, 69.3, 68.7, 65.2, 61.7, 34.1, 34.0, 31.9, 29.7, 29.7, 29.6, 29.5, 29.5, 29.4, 29.3, 29.3, 29.2, 29.1, 24.9, 24.7, 22.7, 20.8, 20.7, 20.7, 20.6 (2 × C), 20.5, 20.5, 14.1; LRMS (ES⁺): m/z (%) = 1191.7 (100) [M + Na]⁺; HRMS (ES⁺): m/z [M + Na]⁺ calcd for C₆₂H₁₀₄O₂₀Na: 1191.7019; found: 1191.7043.

Data for β-peracetate 15: Oil; R _f = 0.67 (PE-EtOAc, 6:4); [α]_D ^²0 -20.0 (c 0.73, CHCl₃); IR (neat): 2923.1, 2853.6, 1753.3, 1369.4, 1225.5, 1043.8 cm^-¹; ^¹H NMR (400 MHz, CDCl₃): δ = 5.58 (dd, J = 3.2, 0.8 Hz, 1 H, H-2′), 5.41 (t, J = 10.4 Hz, 1 H, H-4), 5.39 (t, J = 10.0 Hz, 1 H, H-6), 5.23 (t, J = 10.0 Hz, 1 H, H-4′), 5.11 (t, J = 9.6 Hz, 1 H, H-5), 5.10-5.05 (m, 2 H, H-3 and H-3′), 4.70 (dd, J = 10.4, 2.4 Hz, 1 H, H-1), 4.67 (d, J = 0.8 Hz, 1 H, H-1′), 4.51 (t, J = 2.8 Hz, 1 H, H-2), 4.23 (dd, J = 12.4, 6.0 Hz, 1 H, H-6′a), 4.05 (dd, J = 12.4, 2.4 Hz, 1 H, H-6′b), 3.57 (ddd, J = 10.0, 6.4, 1.6 Hz, 1 H, H-5′), 2.40-2.30 (m, 2 H, H-2′′), 2.29-2.23 (m, 2 H, H-2′′′), 2.27 (s, 3 H), 2.09 (s, 3 H), 2.03 (s, 3 H), 2.01 (s, 3 H), 2.00 (s, 3 H), 2.00 (s, 3 H), 1.97 (s, 3 H), 1.63-1.54 (m, 4 H, H-3′′ and H-3′′′), 1.33-1.22 (m, 56 H), 0.88 (t, J = 6.8 Hz, 6 H, H-18′′ and H-18′′′); ^¹³C NMR (101 MHz, CDCl₃): δ = 173.4, 172.5, 169.84, 169.78, 169.76, 169.6, 169.5, 169.4, 169.3, 99.5, 76.4, 70.6, 70.4, 69.6 (3 × C), 69.5, 69.3, 68.7, 65.2, 61.7, 34.1, 34.0, 31.9, 29.7, 29.7, 29.6, 29.5, 29.5, 29.4, 29.3, 29.3, 29.2, 29.1, 24.9, 24.7, 22.7, 20.8, 20.7, 20.7, 20.6 (2 × C), 20.5, 20.5, 14.1; LRMS (ES⁺): m/z (%) = 1191.7 (100) [M + Na]⁺; HRMS (ES⁺): m/z [M + Na]⁺ calcd for C₆₂H₁₀₄O₂₀Na: 1191.7019; found: 1191.7015.