SYNTHESIS
Papers
1286
(10 mL) was added, the inorganic salts were filtered off, and the sol-
vent was evaporated in vacuo. The residue was purified by flash chro-
matography (silica gel, Et2O/pentane 1:2) to yield 141 mg (53%) of
the dioxolane 28d;
(b) Gmeiner, P.; Junge, D.; Kärtner, A. J. Org. Chem. 1994, 59,
6766.
(10) Guarnieri, W. Diploma Thesis, Universität Kiel 1992.
(11) (a) Beau, J.-M.; Sinaÿ, P. Tetrahedron Lett. 1985, 26, 6189.
(b) Beau, J.-M.; Sinaÿ, P. Tetrahedron Lett. 1985, 26, 6192.
(12) Another example of migration of the 4-O-carbamoyl group was
observed for the lithiated pentane-1,4-diyl carbamate; Ahrens,
H. Dissertation, Universität Kiel 1994.
oil; Rf 0.74 (Et2O); [α]D20 +41.5 (c = 1.33, CHCl3).
IR (film): ν = 3400 (OH), 1740 cm–1 (C=O).
1H NMR (CDCl3, 300 MHz): δ = 0.90 [s, 9H, C(CH3)3]; 2.21 (m, 6-
H); 2.75 (m, 6-H); 2.83 (ddd, 3J4,5 = 8.3 Hz, 3J5,6 = 6.0 Hz, 3J5,6 = 5.6
Hz, 5-H); 2.92 (dd, 4-H); 3.45 (d, 2H, 2J = 13.2 Hz, NCH2Ph); 3.51
(13) Ref. 5a, and references cited therein.
3
(d, J3,4 = 7.9 Hz, 3-H); 3.85 (d, 2H, NCH2Ph); 4.15 (m, 2H, 7-H);
(14) Hoppe, D.; Paetow, M.; Hintze, F. Angew. Chem. 1993, 105,
430; Angew. Chem., Int. Ed. Engl. 1993, 32, 394.
(15) Gutierrez, C. G.; Stringham, R. A.; Nitasaka, T.; Glasscock, K.
G. J. Org. Chem. 1980, 45, 3393.
(16) Sendzik, M.; Guarnieri, W.; Hoppe, D. Synthesis 1998, 1287.
(17) (a) Cohen, T.; Lin, M.-T. J. Am. Chem. Soc., 1984, 106, 1130.
(b) Cohen, T.; Sherbine, J. P.; Matz, J. R.; Hutchins, R. R.;
McHenry, B. M.; Willey, P. R. J. Am. Chem. Soc. 1984, 106,
3245.
7.30 (m, 10H, Ph).
13C NMR (CDCl3, 75 MHz): δ = 25.95 (C-6); 26.17 [3C, C(CH3)3];
35.30 (C-2); 57.73 (C-5); 64.33 (2C, NCH2Ph); 66.28 (C-7); 68.23
(C-4); 77.35 (C-3); 127.79, 128.61, 128.85, 129.29, 129.49, 129.53,
129.60, 138.46 (Ph); 155.33 (C=O).
Anal. Calcd for C24H31NO4 (397.50): C, 70.52; H, 8.16; N, 3.52.
Found: C, 70.56; H, 8.45; N, 3.75.
(18) Seebach, D.; Pomakotr, M.; Geiss, K.-H. Chem. Ber. 1979, 112,
1420.
Generous support by the Deutsche Forschungsgemeinschaft and the
Fonds der Chemischen Industrie is gratefully acknowledged.
(19) Low diastereoselectivity has been observed in carbonyl additi-
ons of sp3 organometallic compounds, see, e.g.: Devant, R. M;
Radunz, H.-E. In Houben Weyl, 4th ed., Vol. E 21b; Helmchen,
G.; Hoffmann, R. W.; Mulzer, J.; Schaumann, E., Eds.; Thieme:
Stuttgart, 1995; pp 1269–1296.
(20) Guarnieri, W. Dissertation, Universität Münster 1995.
(21) X-ray crystal structure analysis of 32: formula C25H35NO23, M
= 397.54, 1.00 × 0.15 × 0.10 mm, a = 9.080(1), b = 7.463(1), c
(1) (a) Kuhn, R. Angew. Chem. 1957, 69, 23.
(b) Nakanishi, K.; Goto, T.; Ito, S.; Natori, S.; Nozoe S. Natural
Products Chemistry, Vol. 3; Oxford University Press: Oxford,
1983.
(c) Kennedy, J. F.; White, C. A. Bioactive Carbohydrates; Ellis
Horwood: Chichester, 1983.
(d) Ohfune, Y. Acc. Chem. Res. 1992, 25, 360.
(e) Kunieda, T.; Ishizuka, T. In Studies in Natural Products
Chemistry, Vol. 12; Atta-ur-Rahman, Ed.; Elsevier: New York,
1993, pp 411-444.
= 17.032(2) Å, β = 101.44(1), V = 1131.2(2) Å3, ρ
= 1.167
calc
g cm–3, µ = 5.93 cm–1, Z = 2, monoclinic, space group P21 (No.
4), λ = 1.54178 Å, T = 223 K, ω/2θ scans, 2656 reflections
collected (+h, +k, ±l), [(sinθ)/λ] = 0.62 Å–1, 2499 independent
and 2209 observed reflections [I ≥2 σ(I)], 267 refined parame-
ters, R = 0.038, wR2 = 0.103, max. residual electron density 0.18
(–0.18) e Å–3, Flack parameter 0.0(3), hydrogens calculated and
riding.
(f) Golebiowski, A.; Jurczak, J. Synlett 1993, 241.
(2) (a) Reetz, M. T.; Drewes, M. W.; Schmitz, A. Angew. Chem.
1987, 99, 1186; Angew. Chem., Int. Ed. Engl. 1987, 26, 1141.
(b) Reetz, M. T. Angew. Chem. 1991, 103, 1559; Angew. Chem.,
Int. Ed. Engl. 1991, 30, 1531.
Data set was collected with an Enraf Nonius CAD4 diffrac-
tometer. Programs used: data reduction MolEN, structure solu-
tion SHELXS-86, structure refinement SHELXL-93, graphics
SCHAKAL-92.
Crystallographic data (excluding structure factors) for the struc-
tures reported in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary
publication CCDC-100860. Copies of the data can be obtained
free of charge on application to The Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK [fax: int. code +44(1223)336-
033, E-mail: deposit@ccdc.cam.ac.uk].
(3) (a) Schwerdtfeger, J.; Hoppe, D. Angew. Chem. 1992, 104,
1547; Angew. Chem., Int. Ed. Engl. 1992, 31, 1505.
(b) Boie, C.; Hoppe, D. Synthesis 1997, 176.
(c) Hense, T.; Hoppe, D. Synthesis 1997, 1394.
(4) (a) Hoppe, D.; Hintze, F.; Tebben, P. Angew. Chem. 1990, 102,
1457; Angew. Chem., Int. Ed. Engl. 1990, 29, 1422.
(b) Hintze, F.; Hoppe, D. Synthesis 1992, 1216.
(5) Reviews: (a) Hoppe, D.; Hense, T. Angew. Chem. 1997, 109,
2376; Angew. Chem., Int. Ed. Engl. 1997, 36, 2282.
(b) Hoppe, D.; Hintze, F.; Tebben, P.; Paetow, M.; Ahrens, H.;
Schwerdtfeger, J.; Sommerfeld, P.; Haller, J.; Guarnieri, W.;
Kolczewski, S.; Hense, T.; Hoppe, I. Pure Appl. Chem. 1994,
66, 1479.
(22) Vavon, G.; Conia, J. C. R. Hebd. Séances Acad. Sci. 1946, 223,
245.
(23) Reetz, M. T.; Maier, W. F. Angew. Chem. 1978, 90, 50; Angew.
Chem., Int. Ed. Engl. 1978, 17, 47.
(c) Hoppe, D.; Ahrens, H.; Guarnieri, W.; Helmke, H.; Kol-
czewski, S. Pure Appl. Chem. 1996, 68, 613.
(d) Beak, P.; Basu, A.; Gallagher, D. J.; Park, Y. S.; Thayu-
manavan, S. Acc. Chem. Res. 1996, 29, 552.
(24) Sendzik, M. Diploma Thesis, Universität Münster 1995.
(25) (a) Wigfield, D. C.; Phelps, D. J. J. Am. Chem. Soc. 1974, 96,
543.
(b) Ashby, E. C.; Laemmle, T. Chem. Rev. 1975, 75, 521.
(c) Griffin, G. W. J. Am. Chem. Soc. 1980, 102, 5128.
(26) Masamune, S., Choy, W.; Petersen, J. S.; Sita, L. R. Angew.
Chem. 1985, 97, 1; Angew. Chem., Int. Ed. Engl. 1985, 24, 1.
(27) Solid electrophiles were dissolved in the same solvent (2 mL).
(28) Höfle, G.; Steglich, W. Synthesis 1972, 619.
(29) The diastereomers could not be separated.
(6) For reviews on directed lithiation see:
(a) Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986, 19, 356.
(b) Snieckus, V. Chem. Rev. 1990, 90, 879.
(c) See ref. 5d.
(7) Preliminary communication: Guarnieri, W.; Grehl, M.; Hoppe,
D. Angew. Chem. 1994, 106, 1815; Angew. Chem., Int. Ed.
Engl. 1994, 33, 1734.
(8) Velluz, L.; Amiard, G.; Heymes, R. Bull. Soc. Chim. Fr. 1954,
1012.
(30) Minor diastereomer.
(31) Assignment interchangeable.
(9) 2 and 3 have independently been prepared, see:
(a) Gmeiner, P.; Kärtner, A.; Junge, D. Tetrahedron Lett. 1993,
34, 4325.