Subscribe to RSS
DOI: 10.1055/s-2007-965928
Chain-Elongation of Sugar Aldehydes by Asymmetric Homoaldol Reaction: Introduction of a Functionalized 3-Methyl-Substituted Three-Carbon Unit
Publication History
Publication Date:
08 February 2007 (online)

Abstract
O-Protected aldehydo-sugars reacted with α-titanated crotyl N,N-diisopropylcarbamate to furnish chain-elongated alk-1-enyl carbamates. These were further functionalized by epoxidation of the double bond and subsequent methanolysis to form methyl 3-C-methyl-3-deoxy-furanosides. Mukaiyama-type addition of benzaldehyde led to tetrasubstituted tetrahydrofurans. All reactions proceeded with high diastereoselectivities and allow for a broad application.
Key words
homoaldol reaction - epoxides - (-)-sparteine-mediated metalation - stereoselective synthesis - branched carbohydrates
- 2a
Binder WH.Prenner RH.Schmid W. Tetrahedron 1994, 50: 749 - 2b
Burgos CH.Canales E.Matos K.Soderquist JA. J. Am. Chem. Soc. 2005, 127: 8044 - 2c
Maier P.Redlich H.Richter J. Tetrahedron 2005, 16: 3848 - 2d
Chemler SR.Roush WR. J. Org. Chem. 2003, 68: 1319 - 2e
Casiraghi G.Colombo L.Rassu G.Spanu P. J. Org. Chem. 1990, 55: 2565 - 3a
Hoppe D.Zschage O. Angew. Chem., Int. Ed. Engl. 1989, 26: 69 ; Angew. Chem. 1989, 101, 67 - 3b
Paulsen H.Graeve C.Hoppe D. Synthesis 1996, 141 - 4
Hoppe D.Hanko R.Brönneke A.Lichtenberg F.van Hülsen E. Chem. Ber. 1985, 118: 2822 - For reviews, see:
- 5a
Hoppe D.Hense T. Angew. Chem., Int. Ed. Engl. 1997, 36: 2282 ; Angew. Chem. 1997, 109, 2376 - 5b
Hoppe D.Marr F.Brüggemann M. Top. Organomet. Chem. 2003, 5: 61 - 5c
Christoph G.Hoppe D. In The Chemistry of Organolithium CompoundsRappoport Z.Marek I. Wiley; Chichester: 2004. p.1055 - 6a
Hoppe D.Hanko R.Brönneke A.Lichtenberg F.van Hülsen E. Chem. Ber. 1985, 118: 2822 - 6b
Hanko R.Rabe K.Dally R.Hoppe D. Angew. Chem., Int. Ed. Engl. 1991, 30: 1690 ; Angew. Chem. 1991, 103, 1725 - 6c
Rehders F.Hoppe D. Synthesis 1992, 859 - 6d
Grieco PA.Oguri T.Yokoyama Y. Tetrahedron Lett. 1978, 419 - 6e
Hoppe D.Brönneke A. Tetrahedron Lett. 1983, 24: 1687 - 7a
Hoppe D.Lüßmann J.Jones PG.Schmidt D.Sheldrick GM. Tetrahedron Lett. 1986, 27: 3591 - 7b
Sharpless KB.Verhoeven T. Aldrichimica Acta 1979, 12: 63 - 7c
Wang Z.Schreiber SL. Tetrahedron Lett. 1990, 31: 31 - 7d
Torres G.Torres W.Prieto JA. Tetrahedron 2004, 60: 10245 - 7e
Ohshima T. Chem. Pharm. Bull. 2004, 52: 1031 - For reviews see:
- 7f
Sharpless KB. Angew. Chem. Int. Ed. 2002, 41: 2024 ; Angew. Chem. 2002, 114, 2126 - 7g
Sharpless KB.Johnson RA. In Catalytic Asymmetric SynthesisOjima I. Wiley-VCH; New York: 2000. 2nd ed.. p.231 - 7h
Marco-Contelles I.Molina MT.Anjum S. Chem. Rev. 2004, 104: 2857 - 7i
Katsuki T. Curr. Org. Chem. 2001, 5: 663 - 8
Hoppe D.Tarara G.Wilckens M. Synthesis 1989, 83 - 9a
Hoppe D.Krämer T.Freire Erdbrügger C.Eggert E. Tetrahedron Lett. 1989, 30: 1233 - 9b
Paulsen H.Graeve C.Hoppe D. Synthesis 1996, 145 - 9c
Ünaldi S.Özlügedik M.Fröhlich R.Hoppe D. Adv. Synth. Catal. 2005, 347: 1621 - 9d
Brüns A.Wibbeling B.Fröhlich R.Hoppe D. Synthesis, 2006, 3111 - For related reactions, see:
- 10a
Hoffmann RW.Giesen V.Fuest M. Liebigs Ann. Chem. 1993, 629 - 10b
Mohr P. Tetrahedron Lett. 1993, 34: 6251 - 10c
Hanaki N.Link JT.McMillan DWC.Overman LE.Trankle WG.Wurster JA. Org. Lett. 2000, 2: 223 - 10d
Mukaiyama T.Kobayashi S. Org. React. 1994, 46: 1 - 10e
Mukaiyama T. Tetrahedron 1999, 55: 8609 - 10f
Mukaiyama T. Angew. Chem. Int. Ed. 2004, 43: 5590 ; Angew. Chem. 2004, 116, 5708 - 11a
Martinez MM.Hoppe D. Eur. J. Org. Chem. 2005, 1427 - 11b
Razon P.Dhulut S.Bezzenine-Lafollé S.Courtieu J.Pancrazi A.Ardisson J. Synthesis 2005, 109 - 11c
Martinez MM.Hoppe D. Org. Lett. 2004, 6: 3743 - 11d
Menges M.Brückner R. Eur. J. Org. Chem. 1998, 1023 - 11e
Berque I.Le Ménez P.Razon P.Anis C.Pancrazi A.Ardisson J.Neuman A.Prangé T.Brion J.-D. Synlett 1998, 1132 - 11f
Berque I.Le Ménez P.Razon P.Pancrazi A.Ardisson J.Brion J.-D. Synlett 1998, 1135 - 11g
Le Ménez P.Firmo N.Fargeas V.Ardisson J.Pancrazi A. Synlett 1994, 995 - 11h
Le Ménez P.Fargeas V.Ardisson J.Pancrazi A. Synlett 1994, 998 - 11i
Le Ménez P.Fargeas V.Ardisson J.Lallemand J.-Y.Pancrazi A. Tetrahedron Lett. 1994, 42: 995 - 11j
Zschage O.Hoppe D. Tetrahedron 1992, 48: 5657 - 11k
Paulsen H.Hoppe D. Tetrahedron 1992, 48: 5667 - 11l
Férézou JP.Julia M.Khourzom R.Pancrazi A.Robert P. Synlett 1991, 611 - 12a
Nakata M.Ikeyama Y.Takao M.Kinoshita M. Bull. Chem. Soc. Jpn. 1980, 53: 3252 - 12b
Nakata M.Toshima K.Kai T.Kinoshita M. Bull. Chem. Soc. Jpn. 1985, 58: 3457 - 13
Tarara G.Hoppe D. Synthesis 1989, 89 - 14a
Tipson RS.Cohen A. Carbohydr. Res. 1968, 7: 232 - 14b
Jackson DY. Synth. Commun. 1988, 18: 337 - 15a
Schmidt OT. Methods Carbohydr. Chem. 1963, 2: 318 - 15b
Czernecki S.Dieulesaint A.Valery J.-M. J. Carbohydr. Chem. 1986, 5: 469 - 16a
Szarek MA.Wu X.Szarek WA. Carbohydr. Res. 1997, 299: 165 - 16b
Swern D. J. Org. Chem. 1978, 43: 2480 - 17
Redlich H.Kölln O. Synthesis 1995, 1376 - 18
Jones R.Williams DJ.Kabe Y.Masamune S. Angew. Chem., Int. Ed. Engl. 1985, 24: 1 ; Angew. Chem. 1985, 97, 1 - 19
Landmann B.Hoffmann RW. Chem. Ber. 1987, 120: 331 - 20
Hesse M.Meier H.Zeeh B. Spektroskopische Methoden in der organischen Chemie Thieme; Stuttgart: 2002. p.110 - 22
Chang Z.-Y.Coates RM. J. Org. Chem. 1990, 55: 3475 - 23
Brigl P. Z. Physiol. Chem. 1922, 122: 245 - 24
Ünaldi S.Fröhlich R.Hoppe D. Synthesis 2005, 15 - 27
Peschke B.Lüßmann J.Dyrbusch M.Hoppe D. Chem. Ber. 1992, 125: 1421 - 28a
Lüßmann J.Hoppe D.Jones PG.Fittschen C. Tetrahedron Lett. 1986, 27: 3595 - 28b
Yamamoto H.Sasaki H.Inokawa S. Carbohydr. Res. 1984, 132: 287 - 29
McAuliffe JC.Hindsgaul O. J. Org. Chem. 1997, 62: 1234 - 32
COLLECT
Nonius B.V.;
Delft:
1998.
- 33
Otwinowski Z.Minor W. Denzo-SMN, In Methods in Enzymology, Part A Vol. 276:Carter CW.Sweet RM. Academic Press; London: 1997. p.307-326 - 34a
Blessing RH. Acta Crystallogr., Sect. A 1995, 51: 33 - 34b
Blessing RH. J. Appl. Cryst. 1997, 30: 421 - 35
Otwinowski Z.Borek D.Majewski W.Minor W. Acta Crystallogr., Sect. A 2003, 59: 228 - 36
Sheldrick GM. Acta Crystallogr., Sect. A 1990, 46: 467 - 37
Sheldrick GM. SHELXL-97 University of Göttingen; Göttingen: 1997. - 38
Keller E. SCHAKAL University of Freiburg; Freiburg: 1997.
References
X-ray crystal structure analysis.
21X-ray crystal structure analysis for 16d: Formula C22H39NO7, M = 429.54, colorless crystal 0.40 × 0.30 × 0.30 mm, a = 10.239 (1), b = 12.544 (1), c = 10.305 (1) Å, β = 115.42 (1), V = 1195.4 (2) Å3, ρcalc = 1.193 g cm-3, µ = 0.088 mm-1, empirical absorption correction (0.966 ≤ T ≤ 0.974), Z = 2, monoclinic, space group P21 (No. 4), λ = 0.71073 Å, T = 198 K, ω and φ scans, 11178 reflections collected (± h, ± k, ± l), [(sin θ)/λ] = 0.67 Å-1, 5221 independent (R int = 0.063) and 3783 observed reflections [I ≥ 2 σ (I)], 282 refined parameters, R = 0.045, wR 2 = 0.104, Flack parameter -0.1 (8), max. residual electron density 0.19 (-0.17) e Å-3, hydrogen atoms calculated and refined as riding atoms.
25We isolated and characterized this type of intermediate previously. [8]
26Carbohydrate numberings which matches with those of the open-chain precursor 16.
30X-ray crystal structure analysis for 26c: Formula C23H30O7, M = 418.47, colorless crystal 0.30 × 0.20 × 0.15 mm, a = 10.573 (1), b = 10.872 (1), c = 19723 (1) Å, V = 2267.2 (3) Å3, ρcalc = 1.226 g cm-3, µ = 0.744 mm-1, empirical absorption correction (0.808 ≤ T ≤ 0.897), Z = 4, orthorhombic, space group P212121 (No. 19), λ = 1.54178 Å, T = 293 K, ω and φ scans, 22050 reflections collected (± h, ± k, ± l), [(sin θ)/λ] = 0.60 Å-1, 4065 independent (R int = 0.039) and 3861 observed reflections [I ≥ 2 σ (I)], 276 refined parameters, R = 0.033, wR 2 = 0.089, Flack parameter 0.07 (15), max. residual electron density 0.17 (-0.12) e Å-3, hydrogen atoms calculated and refined as riding atoms.
31Data sets were collected with Nonius KappaCCD diffractometers, in case of Mo-radiation equipped with a rotating anode generator. Programs used: data collection COLLECT, [32] data reduction Denzo-SMN, [33] absorption correction SORTAV [34] and Denzo, [35] structure solution SHELXS-97, [36] structure refinement SHELXL-97, [37] and graphics SCHAKAL. [38] CCDC 621679 & 621680 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033, E-mail: deposit@ccdc.cam.ac.uk].