Abstract
Two different approaches, with an unsaturated carbohydrate as a radical acceptor and a carbohydrate derived aldehyde as a radical precursor, led to key intermediates in the synthesis of 3-deoxy-d -oct-2-ulosonic acids (KDO). Manganese(III) acetate and cerium(IV) ammonium nitrate were the reagents of choice for the oxidative generation of radicals, whereas samarium(II) iodide was employed for reductive couplings. Both strategies were realized by using easily available starting materials, with acetic acid as C2 and ethyl acrylate as C3 building blocks, respectively.
Key words
carbohydrates - chiral pool - natural products - radical reactions - transition metals
References
1a Unger FM.
Adv. Carbohydr. Chem. Biochem.
1981,
38:
323
1b Alexander C.
Reitschel ET.
Biospektrum
1999,
4:
275
2 Li L.-S.
Wu Y.-L.
Curr. Org. Chem.
2003,
7:
447 , and references cited therein
3a Giese B.
Angew. Chem., Int. Ed. Engl.
1985,
24:
553
3b Giese B.
Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds
Pergamon;
Oxford:
1986.
3c Curran DP.
Synthesis
1988,
417
3d Motherwell WB.
Crich D.
Free Radical Chain Reactions in Organic Synthesis
Academic Press;
London:
1992.
3e Linker T.
Schmittel M.
Radikale und Radikalionen in der Organischen Synthese
Wiley-VCH;
Weinheim:
1998.
4a Giese B.
Linker T.
Muhn R.
Tetrahedron
1989,
45:
935
4b Abel S.
Linker T.
Giese B.
Synlett
1991,
171
4c Giese B.
Linker T.
Synthesis
1992,
46
5a Barton DHR.
Jaszberenyi JC.
Liu W.
Shinada T.
Tetrahedron
1996,
52:
2717
5b Pakulski Z.
Zamojski A.
Tetrahedron
1997,
53:
3723
5c Barton DHR.
De Almeida MV.
Liu W.
Shinada T.
Jaszberenyi JCs.
Dos Santos HF.
Hyaric ML.
Tetrahedron
2001,
57:
8767
6a Linker U.
Kersten B.
Linker T.
Tetrahedron
1995,
51:
9917
6b Linker T.
Kersten B.
Linker U.
Peters K.
Peters E.-M.
von Schnering HG.
Synlett
1996,
468
6c Linker T.
Linker U.
Angew. Chem. Int. Ed.
2000,
39:
902
6d Linker T.
J. Organomet. Chem.
2002,
661:
159
7a Linker T.
Hartmann K.
Sommermann T.
Scheutzow D.
Ruckdeschel E.
Angew. Chem., Int. Ed. Engl.
1996,
35:
1730
7b Linker T.
Sommermann T.
Kahlenberg F.
J. Am. Chem. Soc.
1997,
119:
9377
7c Gyóllai V.
Schanzenbach D.
Somsák L.
Linker T.
Chem. Commun.
2002,
1294
7d Sommermann T.
Kim BG.
Peters K.
Peters E.-M.
Linker T.
Chem. Commun.
2004,
2624
8a Snider BB.
Chem. Rev.
1996,
96:
339
8b Melikyan GG.
Org. React.
1997,
49:
427
8c Linker T.
J. Prakt. Chem.
1997,
339:
488
8d Snider BB. In Radicals in Organic Synthesis
Vol. 1:
Renaud P.
Sibi M.
Wiley-VCH;
Weinheim:
2001.
p.198
9 Hartmann K.
Kim BG.
Linker T.
Synlett
2004,
2728
10 Aspinall GO.
Carpenter RC.
Khondo L.
Carbohydr. Res.
1987,
165:
281
11 Peters K.
Peters E.-M.
Hartmann K.
Kim BG.
Linker T.
Z. Kristallogr. - New Cryst. Struct.
2004,
219:
461
12 The supplementary crystallographic data for this structure (CCDC 262607) can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/products/csd/request.
13a Collins PM.
Overend WG.
Shing T.
J. Chem. Soc., Chem. Commun.
1981,
1139
13b Shing TKM.
Tetrahedron: Asymmetry
1994,
5:
2405
13c Railton CJ.
Clive DLJ.
Carbohydr. Res.
1996,
281:
69
14a Nair V.
Mathew J.
Prabhakaran J.
Chem. Soc. Rev.
1997,
127
14b Linker T. In Radicals in Organic Synthesis
Vol. 1:
Renaud P.
Sibi M.
Wiley-VCH;
Weinheim:
2001.
p.219
14c Nair V.
Balagopal L.
Rajan R.
Mathew J.
Acc. Chem. Res.
2004,
37:
21
15 The supplementary crystallographic data for this structure (CCDC 263264) can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/products/csd/request.
16a Curran DP.
Porter NA.
Giese B.
Stereochemistry of Radical Reactions
VCH;
Weinheim:
1996.
16b Giese B. In Radicals in Organic Synthesis
Vol. 1:
Renaud P.
Sibi M.
Wiley-VCH;
Weinheim:
2001.
p.381
16c Sibi MP.
Manyem S.
Zimmerman J.
Chem. Rev.
2003,
103:
3263
17 Arai N.
Narasaka K.
Bull. Chem. Soc. Jpn.
1997,
70:
2525
18a Molander GA.
Org. React.
1994,
46:
211
18b Molander GA.
Chem. Rev.
1996,
96:
307
18c Krief A.
Laval A.-M.
Chem. Rev.
1999,
99:
745
18d Molander GA. In Radicals in Organic Synthesis
Vol. 1:
Renaud P.
Sibi M.
Wiley-VCH;
Weinheim:
2001.
p.153
18e Kagan HB.
Tetrahedron
2003,
59:
10351
18f Edmonds DJ.
Johnston D.
Procter DJ.
Chem. Rev.
2004,
104:
3371
19a Fukuzawa S.
Nakanishi A.
Fujinami T.
Sakai S.
J. Chem. Soc., Chem. Commun.
1986,
624
19b Otsubo K.
Inanaga J.
Yamaguchi M.
Tetrahedron Lett.
1986,
27:
5783
19c Kawatsura M.
Matsuda F.
Shirahama H.
J. Org. Chem.
1994,
59:
6900
19d Matsuda F.
Kawatsura M.
Dekura F.
Shirahama H.
J. Chem. Soc., Perkin Trans. 1
1999,
2371
19e Kerrigan NJ.
Upadhyay T.
Procter DJ.
Tetrahedron Lett.
2004,
45:
9087
20 Regeling H.
de Rouville E.
Chittenden JF.
Recl. Trav. Chim. Pays-Bas
1987,
106:
461
21 Sheldrick GM.
SHELXS-86, Program for the Solution of Crystal Structures
University of Göttingen;
Germany:
1985.
22 Sheldrick GM.
SHELXL-97, Program for Crystal Structure Refinement
University of Göttingen;
Germany:
1997.
