[Zinc-Diamine]-Catalyzed Hydrosilylation of Ketones
FULL PAPERS
(
CꢀF), 1363 (s, OꢀCH ), 1116 (vs, CꢀO); anal. calcd. for ZnC
References and Notes:
2
2
H OF (165.5): C 14.51, H 1.81; found: C 16.68, H 1.79.
3
3
A 85 mg (0.514 mmol) sample of 18 produced 10.5 mL
0.429 mmol) of gas (H ) at 258C, 1 atm when hydrolyzed
with acidified water. Removing of volatiles from the filtrate
[
1] a) B. A. Astelford, L. O. Weigel, in: Chirality in Industry
II, (Ed.: A. N. Collins), Wiley, New York, 1997, p. 99;
b) S. C. Stinson Chem. Eng. News 2000, 78, 55–79;
c) M. Breuer, K. Ditrich, T. Habicher, B. Hauer, M. Keb-
eler, R. Sturmer, T. Zelinski, Angew. Chem. Int. Ed.
2004, 43, 788.
2] For recent reviews on chemo- and enantioselective hy-
drosilylation, see: a) H. Brunner, in Transition Met.
Org. Synth., (Eds.: M. Beller, C. Bolm), 1998, Vol. 2, p.
131; b) J.-F. Carpentier, V. Bette, Curr. Org. Chem.
2002, 6, 913–936; c) H. Nishiyama, in: Comprehensive
Asymmetric Catalysis, Vol. 1 (Eds.: E. N. Jacobsen, A.
Pfaltz, H. Yamamoto), Springer, Berlin, 1999, pp. 267–
287; d) T. Ohkuma; R. Noyori, Comp. Asym. Catal.
Supp. 2004, 1, 55–71.
(
2
gave a colorless oil, identified according to ES-MS as the silox-
1
ane 19; yield: 60 mg (38%); H NMR (toluene-d ): d¼7.50 (d,
8
J¼7.3 Hz, 2H, arom.), 7.10 (d, J¼7.3 Hz, 3H, arom.), 3.67
1
3
1
(
q, J¼8.3 Hz, 6H, CH CF ); C{ H} NMR (toluene-d ): d¼
2
3
8
[
1
35.0 (C arom.), 132.32 (C arom.), 129.3 (C arom.), 128.7 (C
1
arom.), 128.4 (C arom.), 127.5 (C arom.), 124.1 (q, J
78.6 Hz, CF ), 61.4 (q,
¼
C,F
2
2
JC,F ¼36.8 Hz, CH CF );
3
2
3
1
9
1
F{ H} NMR (toluene-d ): d¼ ꢀ71.86; MS (electrospray, di-
8
rect introduction): m/z¼622 (M).
Reaction of [Zn(dbea)(OCH CF ) ] (15a) with PhSiH
3
2
3
2
1
) Reaction with 1 equiv. of PhSiH : In the glove-box, PhSiH
3
3
[
3] a) For a review on PMHS see: N. J. Lawrence, M. D.
Drew, S. M. Bushell, J. Chem. Soc. Perkin Trans. 1
(
12.5 mL, 0.10 mmol, 1.0 equiv. vs. Zn) was added to a solution
of [Zn(dbea)(OCH CF ) ] (15a) (51 mg, 0.10 mmol) in tol-
2
3 2
1
999, 3381–3391; for the use of PMHS in hydrosilylation,
uene-d (ca. 1.0 mL) placed in an NMR tube. Upon addition
8
see: b) M. T. Reding, S. L. Buchwald, J. Org. Chem. 1995,
60, 7884–7890; c) Y. Kobayshi, E. Takahisa, M. Nakano,
K. Watatani, Tetrahedron 1997, 53, 1627–1634; d) M. D.
Drew, N. J. Lawrence, D. Fontaine, L. Sehkri, Synlett
1997, 989–991; e) M. D. Drew, N. J. Lawrence, W. Wat-
son, S. A. Bowles, Tetrahedron Lett. 1997, 38, 5857–
of the silane, a fine white precipitate formed immediately
and gas evolution was observed. A grey deposit formed after
a few hours which was filtered off on a short celite bed. Remov-
al of volatiles from the clear filtrate gave a yellow oil that was
analyzed by NMR as a mixture of free dbea and an unidentified
1
silylated species. H NMR (toluene-d ): d¼7.50 (d, J¼6.4 Hz,
8
2
H, arom., SiPh), 7.30–6.90 (m, 10H arom., dbeaþ3H arom.,
5
860; f) X. Verdaguer, M. C. Hansen, S. C. Berk, S. L.
SiPh), 4.49 (s, weak), 4.18 (s, weak), 3.68 (q, J¼8.3 Hz, 4H,
OCH CF ), 3.56 (d, J¼6.3 Hz, 4H, NHCH Ph, dbea), 2.49
Buchwald, J. Org. Chem. 1997, 62, 8522–8528; g) J.
Yun, S. L. Buchwald, J. Am. Chem. Soc. 1999, 121,
5640–5644; h) N. J. Lawrence, S. M. Bushell, Tetrahedron
Lett. 2000, 41, 4507–4512; i) M. C. Hansen, S. L. Buch-
wald, Org. Lett. 2000, 2, 713–715; j) X. Huang, K. W. An-
derson, D. Zim, L. Jiang, A. Klapars, S. L. Buchwald, J.
Am. Chem. Soc. 2003, 125, 10767; k) V. Jurkauskas, J. P.
Sadighi, S. L. Buchwald, Org. Lett. 2003, 5, 2417–2420;
l) B. H. Lipshutz, J. M. Servesko, Angew. Chem. Int.
Ed. 2003, 42, 4789–4792; m) B. H. Lipshutz, K. Noson,
W. Chrisman, A. Lower, J. Am. Chem. Soc. 2003, 125,
8779–8789; n) B. H. Lipshutz, J. M. Servesko, T. B. Pe-
tersen, P. P. Papa, A. A. Lover, Org. Lett. 2004, 6,
2
3
2
(
br s, 4H, CH NHBn, dbea), 1.09 (br s, 2H, NH, dbea);
2
1
3
1
C{ H} NMR (toluene-d ): d¼141.5 (C arom.), 135.0 (C
8
arom.), 132.2 (C arom.), 129.3 (C arom.), 128.8 (C arom.),
1
28.7 (C arom.), 128.4 (C arom.), 128.3 (C arom.), 127.48 (C
1
arom.), 126.9 (C arom.), 128.1 (q, J ¼246.6 Hz, CF ), 61.4
C,F
3
2
(
(
q, J ¼36.9 Hz, OCH CF ), 54.2 (NHCH Ph dbea), 49.3
C,F
2
3
2
19 1
CH NHBn dbea); F{ H} NMR (toluene-d ): d¼ ꢀ71.80.
2
8
2
) Reaction with 0.33 equivs. of PhSiH : In the glove-box,
3
PhSiH (4.5 mL, 0.037 mmol, 0.33 equivs. vs. Zn) was added
3
to
a solution of [Zn(dbea)(OCH CF ) ] (15a) (56 mg,
2 3 2
0
.109 mmol) in toluene-d (ca. 1 mL) placed in an NMR tube.
8
A white cloudiness formed transiently with the addition of
1
the silane, but no precipitate was observed. H NMR (tol-
1
273–1275; o) use of Lewis acid catalysts: N. Asao, T.
Ohishi, K. Sato, Y. Yamamoto, Tetrahedron 2002, 58,
195–8203; p) Z. Wang, A. E. Wroblewski, J. G. Ver-
kade, J. Org. Chem. 1999, 64, 8021–8023.
[4] H. Mimoun, J. Org. Chem. 1999, 64, 2582–2589.
uene-d ): d¼7.50 (d, J¼6.0 Hz, 2H, arom., SiPh), 7.30–6.90
8
(
m, 10H, arom., dbeaþ3H, arom., SiPh), 4.50 (s, 1H, Zn-H
8
[
20]?), 4.0 (br s, 4H, OCH CF [20]), 3.65 (q, J¼8.3 Hz, 4H,
2
3
OCH CF [19]), 3.55 (d, J¼6.3 Hz, 4H, NHCH Ph [20]), 2.3
2
3
2
1
3
1
(
br s, 4H, CH NHBn [20]); C{ H} NMR (toluene-d ): d¼
2
8
[
5] H. Mimoun, J. Y. Saint Laumer, L. Giannini, R. Scopel-
liti, C. Floriani, J. Am. Chem. Soc. 1999, 121, 6158–6166.
1
35.0 (C arom.), 128.7 (C arom.), 128.2 (C arom.), 125.4 (C
1
2
arom.), 125. 4 (q, JC,F ¼268.7 Hz, CF ), 65.4 (q, JC,F
¼
3
2
3
3.4 Hz, OCH CF [20]), 61.4 (q, J ¼36.9 Hz, OCH CF
[6] a) V. M. Mastranzo, L. Quintero, C. Anaya de Parrodi,
E. Juaristi, P. J. Walsh, Tetrahedron 2004, 60, 1781–
1789; b) V. Bette, A. Mortreux, D. Savoia, J.-F. Carpent-
ier, Tetrahedron 2004, 60, 2837–2842; c) V. Bette, A.
Mortreux, D. Savoia, J.-F. Carpentier, Eur. J. Org.
Chem. 2004, 3040–3045.
2
3
C,F
2
3
[
19]), 53.8 (NHCH Ph [20]), 46.6 (CH NHBn [20]);
2
2
1
9
1
F{ H} NMR (toluene-d ): d¼ ꢀ71.84.
8
Acknowledgements
[
7] a) J. Lipowitz, S. A. Bowman, J. Org. Chem. 1973, 38,
62–165; b) J. Lipowitz, S. A. Bowman, Aldrich Chim.
Acta 1973, 6, 1–6.
1
We thank the CNRS and PPG-Sipsy for financial support of this
research (Ph.D. grant to V. B.) We are grateful to Prof. A. Alex-
akis (University of Geneva) for providing us a sample of di-
amine 10.
[8] N. J. Lawrence, S. M. Bushell, Tetrahedron Lett. 2000, 41,
4507–4512.
Adv. Synth. Catal. 2005, 347, 289–302
asc.wiley-vch.de
ꢂ 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
301