LETTER
Dinuclear Titanium–Sulfamide Complexes
2101
sulfamides from SO2Cl2 and primary amines,12,13 the new
precatalysts offer great potential for further optimization.
D. W.; Mason, S.; Moore, M. R.; Fawcett, J.; Russell, D. R.
J. Chem. Soc., Chem. Commun. 1990, 1535.
(12) (a) Parnell, E. W. J. Chem. Soc. 1960, 4366. (b) Bermann,
M.; van Wazer, J. R. Synthesis 1972, 576. (c) Hawkins, J.
M.; Sharpless, K. B. J. Org. Chem. 1984, 49, 3861.
(13) Alternative synthesis of sulfamides can be found in:
(a) Muñiz, K.; Nieger, M. Synlett 2005, 149. (b) Leontiev,
A. V.; Dias, H. V. R.; Rudkevich, D. M. Chem. Commun.
2006, 2887. (c) Woolven, H.; González-Rodríguez, C.;
Marco, I.; Thompson, A. L.; Willis, M. C. Org. Lett. 2011,
13, 4876.
R
R
3 (2.5 mol%)
R
R
NH2
n-hexane
100 °C, 2 h
NH
9: R = Ph: 95%
10: R = Bn: 97%
11: R = Me: –
(14) Experimental Procedure
1) 3 (2.5 mol%)
n-hexane, 100 °C, 2 h
N,N′-Diphenylsulfamide (1, 0.248 g, 1.0 mmol) was slowly
added to a solution of Ti(NMe2)4 (0.224 g, 1.0 mmol) in
toluene (5 mL) at r.t. The reaction mixture was stirred for
3 h, and then the solvent was removed under vacuum. The
resulting solid was recrystallized from a mixture of toluene
and CH2Cl2 (10:3) to give red crystals of complex 2 (0.311
g, 81%). 1H NMR (500 MHz, CDCl3): δ = 3.31 (s, 24 H,
NH2
2) TsCl, Et3N
CH2Cl2, 18 h, r.t.
N
12
Ts
13, 86%
Scheme 3 Hydroamination of various aminoalkenes
CH3), 6.96 (d, 3JH,H = 8.0 Hz, 8 H, PhHortho), 7.01 (t, 3JH,H
=
)
7.3 Hz, 4 H, PhHpara), 7.14 (t, 3JH,H = 7.7 Hz, 8 H, PhHmeta
ppm. 13C NMR (126 MHz, C6D6): δ = 47.7 (CH3), 124.5
(CH), 125.6 (CH), 128.6 (CH), 143.1 (C) ppm.
Acknowledgment
We thank the Deutsche Forschungsgemeinschaft for financial sup-
port of our research.
(15) (a) Armistead, L. T.; White, P. S.; Gagné, M. R.
Organometallics 1998, 17, 216. (b) Royo, E.; Betancort, J.
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4171.
References and Notes
(1) Review: Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo,
F.; Tada, M. Chem. Rev. 2008, 108, 3795.
(2) Review: Roesky, P. W. Angew. Chem. Int. Ed. 2009, 48,
4892; Angew. Chem. 2009, 121, 4988.
(3) (a) Clerici, M. G.; Maspero, F. Synthesis 1980, 305.
(b) Nugent, W. A.; Ovenall, D. W.; Holmes, S. J.
(16) Compound 2: red crystals (polyhedron), dimensions 0.50 ×
0.21 × 0.15 mm3, monoclinic, space group P21/n, unit cell
dimensions: a = 9.0358(2) Å, b = 16.0367(3) Å, c =
12.5598(2) Å, α = 90°, β = 96.6210(10)°, γ = 90°, V =
1807.83(6) Å3, Z = 2, ρ = 1.410 Mg/m3, Θmax= 34.99°,
radiation Mo Kα, λ = 0.71073 Å, φ and ω scans with Bruker
KAPPA APEX-II CCD at T = 153(2) K, 32381 reflections
measured, 7876 unique [Rint = 0.0470], 6067 observed [I >
2σ(I)], intensities were corrected for Lorentz and
Organometallics 1983, 2, 161. (c) Herzon, S. B.; Hartwig, J.
F. J. Am. Chem. Soc. 2007, 129, 6690. (d) Herzon, S. B.;
Hartwig, J. F. J. Am. Chem. Soc. 2008, 130, 14940.
(4) (a) Eisenberger, P.; Ayinla, R. O.; Lauzon, J. M. P.; Schafer,
L. L. Angew. Chem. Int. Ed. 2009, 48, 8361; Angew. Chem.
2009, 121, 8511. (b) Zi, G.; Zhang, F.; Song, H. Chem.
Commun. 2010, 46, 6296. (c) Reznichenko, A. L.; Emge, T.
J.; Audörsch, S.; Klauber, E. G.; Hultzsch, K. C.; Schmidt,
B. Organometallics 2011, 30, 921. (d) Reznichenko, A. L.;
Hultzsch, K. C. J. Am. Chem. Soc. 2012, 134, 3300.
(5) (a) Kubiak, R.; Prochnow, I.; Doye, S. Angew. Chem. Int.
Ed. 2009, 48, 1153; Angew. Chem. 2009, 121, 1173.
(b) Prochnow, I.; Kubiak, R.; Frey, O. N.; Beckhaus, R.;
Doye, S. ChemCatChem 2009, 1, 162. (c) Kubiak, R.;
Prochnow, I.; Doye, S. Angew. Chem. Int. Ed. 2010, 49,
2621; Angew. Chem. 2010, 122, 2683. (d) Prochnow, I.;
Zark, P.; Müller, T.; Doye, S. Angew. Chem. Int. Ed. 2011,
50, 6401; Angew. Chem. 2011, 123, 6525.
(6) Bexrud, J. A.; Eisenberger, P.; Leitch, D. C.; Payne, P. R.;
Schafer, L. L. J. Am. Chem. Soc. 2009, 131, 2116.
(7) (a) Ackermann, L.; Bergman, R. G. Org. Lett. 2002, 4, 1475.
(b) Ackermann, L.; Bergman, R. G.; Loy, R. N. J. Am.
Chem. Soc. 2003, 125, 11956.
(8) (a) Watson, D. A.; Chiu, M.; Bergman, R. G.
Organometallics 2006, 25, 4731. (b) Xiang, L.; Zhang, F.;
Zhang, J.; Song, H.; Zi, G. Inorg. Chem. Commun. 2010, 13,
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polarization effects, an empirical absorption correction was
applied using Bruker SAINT based on the Laue symmetry of
the reciprocal space, μ = 0.611 mm–1, Tmin = 0.7516, Tmax
=
0.9150, structure solved by direct methods and refined
against F2 with a full-matrix least-squares algorithm using
the SHELXS-97 software package, 230 parameters refined,
hydrogen atoms were treated using appropriate riding
models, goodness of fit 1.026 for observed reflections, final
residual values R1 = 0.0341, wR2 = 0.0901 for observed
reflections, largest diff. peak, hole 0.456 and –0.327 eÅ–3.
The structure contains about 4% Cl atoms in the para
position of the phenyl substituents. This is caused by a
chlorination side reaction that takes place during the
synthesis of the ligand 1. However, the impurity could not be
observed by 1H NMR. CCDC number 883164 contains the
supplementary crystallographic data for this paper. These
data can be obtained free of charge from the Cambridge
Crystallographic Data Centre via
(17) Experimental Procedure
N,N′-Diphenylsulfamide (1, 0.612 g, 2.5 mmol) was slowly
added to a solution of Ti(NMe2)4 (1.14 g, 5.1 mmol) in
n-hexane (10 mL) at r.t. The reaction mixture was stirred
for 3 h, and then the dispersed precipitate was filtered off
quickly. The resulting solid was dried under vacuum to give
the pure complex 3 (0.990 g, 65%) as a light yellow powder.
For crystallization, a concentrated solution of 3 in a mixture
of n-hexane and toluene (5:3) was stored at 4 °C to give light
yellow crystals. 1H NMR (500 MHz, C6D6): δ = 3.13 (s, 36
(9) Born, K.; Doye, S. Eur. J. Org. Chem. 2012, 764.
(10) Mills, R. C.; Doufou, P.; Abboud, K. A.; Boncella, J. M.
Polyhedron 2002, 21, 1051.
(11) Pt complexes with sulfamide ligands are described in:
(a) Kemmitt, R. D. W.; Mason, S.; Moore, M. R.; Russell, D.
R. J. Chem. Soc., Dalton Trans. 1992, 409. (b) Kemmitt, R.
© Georg Thieme Verlag Stuttgart · New York
Synlett 2012, 23, 2098–2102