Angewandte
Chemie
13C NMR (125 MHz,CDCl 3): d = 27.9,38.5,47.1,52.4,54.6,83.3,
103.4,115.6 (q, J = 288 Hz),127.5,128.5,129.3,135.2,156.6 (q,
37.7 Hz),168.9,169.1 ppm. Elemental analysis (%) calcd for
Angew.Chem. 2000, 112,248 – 252; Angew.Chem.Int.Ed. 2000,
J =
39,242 – 246; c) C. J. Easton, Chem.Rev. 1997, 97,53 – 82.
[6] a) C. J. Easton,I. M. Scharfbillig,E. W. Tan, Tetrahedron Lett.
1988, 29,1565 – 1568; b) G. Apitz,W. Steglich, Tetrahedron Lett.
1991, 32,3163 – 3166; c) W. Steglich,M. Jäger,S. Jaroch,P.
Zistler, Pure Appl.Chem. 1994, 66,2167 – 2170.
[7] D. Seebach, Angew.Chem. 1988, 100,1685 – 1715; Angew.Chem.
Int.Ed.Engl. 1988, 27,1624 – 1654,and references therein.
[8] a) D. Seebach,A. K. Beck,H. G. Bossler,C. Gerber,S. Y. Ko,
C. W. Murtiashaw,R. Naef,S.-I. Shoda,A. Thaler,M. Krieger,R.
Wenger, Helv.Chim.Acta 1993, 76,1564 – 1590; b) S. A. Miller,
S. L. Griffiths,D. Seebach, Helv.Chim.Acta 1993, 76,563 – 595;
c) C. Paulitz,W. Steglich, J.Org.Chem. 1997, 62,8474 – 8478.
[9] a) G. T. Crisp,P. T. Glink, Tetrahedron Lett. 1992, 33,4649 –
4652; b) G. T. Crisp,P. T. Glink, Tetrahedron 1994, 50,3213 –
3234.
C20H24F3IN2O4 (540.07): C 44.46,H 4.48,N 5.18; found: C 44.68,H
4.33,N 5.24. HPLC (Reprosil 100 Chiral-NR 8 mm,hexane/ iPrOH
99:1,2.0 mLmin ꢀ1,209 nm): t(S,S) = 9.15 min, t(S,R) = 12.03 min.
Synthesis of 13: Dimethylzinc (2m in toluene,0.23 mL,
0.46 mmol) was added to a solution of 8 (81 mg,0.15 mmol),
[{(allyl)PdCl}2] (1.1 mg,3.0 mmol) and PPh3 (1.6 mg,6.0 mmol) in
abs. THF (3 mL) at 08C. After the reaction mixture had been stirred
for 24 h at room temperature, tBuOH (0.5 mL) was added and the
solvents were removed in vacuo. The crude product was purified by
flash chromatography (hexanes/CH2Cl2 6:4) giving 13 (54 mg,
0.126 mmol,84%) as colorless crystals,m.p. (hexane/Et 2O): 1148C.
1
[a]2D0 = + 3.5 (c = 1.0,98% ds,CHCl 3). H NMR (500 MHz,CDCl ):
3
d = 1.35 (s,9H),1.63 (s,3H),2.20 (dd, J = 14.0,7.8 Hz,1H),2.28 (dd,
J = 14.1,6.3 Hz,1H),3.03 (dd,
13.8,6.8 Hz,1H),4.41 (ddd, J = 7.7,7.7,6.3 Hz,1H),4.56 (s,1H),4.64
(ddd, J = 7.7,7.7,6.9 Hz,1H),4.71 (s,1H),6.33 (d, J = 7.7 Hz,1H),
7.11–7.25 (m,5H),7.51 ppm (d, J = 7.7 Hz,1H). 13C NMR (125 MHz,
CDCl3): d = 21.7,27.9,38.6,40.6,51.1,54.7,82.6,114.6,115.8 (q, J =
286 Hz),127.4,128.8,129.3,135.3,140.3,156.6 (q, J = 37.2 Hz),168.8,
J = 13.8,7.5 Hz,1H),3.08 (dd,
J =
[10] a) U. Kazmaier,D. Schauß,M. Pohlman,S. Raddatz, Synthesis
2000,914 – 917; b) U. Kazmaier,D. Schauß,S. Raddatz,M.
Pohlman, Chem.Eur.J. 2001, 7,456 – 464.
[11] a) U. Kazmaier,D. Schauß,M. Pohlman, Org.Lett. 1999, 1,
1017 – 1019; b) U. Kazmaier,M. Pohlman,D. Schauß, Eur.J.
Org.Chem. 2000,2761 – 2766; c) A. O. Wesquet,S. Dörren-
bächer,U. Kazmaier, Synlett 2006,1105 – 1109.
170.5 ppm. Elemental analysis (%) calcd for C21H27F3N2O4 (428.46):
C 58.87,H 6.35,N 6.54; found: C 59.02,H 6.30,N 6.54. HRMS (CI)
calcd for C21H28F3N2O4 [M+H]+: 429.2001; found: 429.2041. HPLC
[12] U. Kazmaier,S. Maier,F. L. Zumpe, Synlett 2000,1523 – 1535.
[13] a) U. Kazmaier, J.Org.Chem.
1994, 59,6667 – 6670; b) U.
(Reprosil 100 Chiral-NR 8 mm,hexane/ iPrOH 99.5/0.5,1.5 mLmin ꢀ1
209 nm): t(S,S) = 16.65 min, t(S,R) = 22.07 min.
,
Kazmaier,S. Maier, Chem.Commun. 1998,2535 – 2536; c) U.
Kazmaier,S. Maier, Org.Lett. 1999, 1,1763 – 1766; d) S. Maier,
U. Kazmaier, Eur.J.Org.Chem. 2000,1241 – 1251.
[14] a) U. Kazmaier,J. Deska,A. Watzke, Angew.Chem. 2006, 118,
Received: February 19,2007
Published online: May 7,2007
4973 – 4976; Angew.Chem.Int.Ed.
2006, 45,4855 – 4858; b) J.
Deska,U. Kazmaier, Chem.Eur.J. 2007, 13,in press.
[15] D. Seebach,V. Prelog, Angew.Chem. 1982, 94,696 – 702; Angew.
Chem.Int.Ed.Engl. 1982, 21,654 – 660.
[16] The selectivities obtained with the stannylated substrates were
significantly better than with the non-metalated analogues (see
Ref. [14]),and therefore we did not examine the influence of the
inducing amino acids in detail.
[17] S. Dörrenbächer,U. Kazmaier,S. Ruf, Synlett 2006,547 – 550.
[18] a) J. K. Stille, Angew.Chem. 1986, 98,504 – 519; Angew.Chem.
Int.Ed.Engl. 1986, 25,508 – 524; b) T. N. Mitchell, Synthesis
1992,803 – 815.
[19] a) E.-I. Negishi,L. Anastasia, Chem.Rev. 2003, 103,1979 – 2017;
b) E.-I. Negishi,Q. Hu,Z. Huang,M. Qian,G. Wang,
Aldrichimica Acta 2005, 38,71 – 88.
[20] a) T. Nishiyama,T. Esumi,Y. Iwabuchi,H. Irie,S. Hatakeyama,
Tetrahedron Lett. 1998, 39,43 – 46; b) K. Kumar,A. Zapf,D.
Michalik,A. Tillack,T. Heinrich,H. Böttcher,M. Arlt,M.
Beller, Org.Lett. 2004, 6,7 – 10; c) J. Xu,D. J. Burton, J.Org.
Chem. 2005, 70,4346 – 4353; d) A. Padwa,S. K. Baur,H. Zhang,
J.Org.Chem. 2005, 70,6833 – 6841.
Keywords: allylation · cross-coupling · palladium ·
peptide modifications · stannanes
.
[1] Reviews: a) M. A. Marahiel,T. Stachelhaus,H. D. Mootz, Chem.
Rev. 1997, 97,2651 – 2673; b) H. von Döhren,U. Keller,J. Vater,
R. Zocher, Chem.Rev. 1997, 97,2675 – 2705.
[2] Reviews: a) D. R. W. Hodgson,J. M. Sanderson, Chem.Soc.Rev.
2004, 33,422 – 430; b) N. Fusetani,S. Matsunaga, Chem.Rev.
1993, 93,1793 – 1806.
[3] Reviews: a) D. Seebach, Aldrichimica Acta 1992, 25,59 – 66;
b) D. Seebach,A. K. Beck,A. Studer in
Modern Synthetic
Methods, Vol.7 (Eds.: B. Ernst,C. Leumann),Helvetica Chimica
Acta,Basel, 1995,pp. 1 – 178.
[4] a) J.-C. Gfeller,A. K. Beck,D. Seebach, Helv.Chim.Acta 1980,
63,728 – 732; b) M. J. Dunn,S. Gomez,R. F. W. Jackson,
Chem.Soc.Perkin Trans.1 1995,1639 – 1640; c) J. Barluenga,
M. A. García-Martín,J. M. Gonzµlez,P. ClapØs,G. Valencia,
Chem.Commun. 1996,1505 – 1506.
J.
[5] a) M. Ricci,P. Blakskjaer,T. Skrydstrup, J.Am.Chem.Soc. 2000,
122,12413 – 12421; b) M. Ricci,L. Madariaga,T. Skrydstrup,
Angew. Chem. Int. Ed. 2007, 46, 4570 –4573
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4573