P. le Floch et al.
sat, 1JPt,P =3686 Hz); 1H NMR (CD2Cl2): d=1.41 (s,6H; CH 3),7.03 (vt,
2H, ꢀJ=16.5 Hz; CHxanthene),7.08–7.17 (m,8H; H meta-Ph),7.18–7.24 (m,
128.0–129.9 (m,C a-phosphole),159.2 (d, 2JP,C =11.6 Hz; CO); elemental anal-
ysis calcd (%) for C50H42O2P2Pt: C 64.44,H 4.54; found: C 64.36,H 4.56.
8H; HPh),7.28 (d,2H,
7.5 Hz; CHxanthene),7.74 ppm (d, 3JH,H =7.7 Hz,8H; H ortho-Ph) ; 13C NMR
(CD2Cl2): d=25.5 (CH3),38.7 (CH3)2),126.1 (vt, ꢀJ=7.7 Hz;
3JH,P =21.1 Hz,H b-phosphole),7.41 (d,2H,
3JH,H
=
X-ray crystallography of 2–5 and7 : Crystals were grown as described in
the text for 3, 5,and 7,and as in the Experimental Section for 2 and 4.
Data were collected on a Nonius Kappa CCD diffractometer with graph-
ite-monochromated MoKa radiation (l=0.71073 ) at 150 K. The crystal
structures were solved with SIR 97[59] and SHELXL97,[60] and ORTEP
drawings were made with ORTEP III for Windows.[61] CCDC-687179 (2),
CCDC-687180 (3),CCDC-687181 ( 4),CCDC-687182 ( 5),and CCDC-
687183 (7) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cambridge
(
C
ACHTREUNG
CHxanthene),127.8 (C Ph),128.3 (C Ph),128.4 (C Ph),129.0 (C Ph),129.4 (C Ph),
134.0 (vt, ꢀJ=13.3 Hz; CxantheneP),136.4 (vt, ꢀJ=12.6 Hz; Cb-phosphole),
138.7 (CPh),148.1 (d, 3JP,P =64.3 Hz; Ca-phosphole),159.4 ppm (CO); elemen-
tal analysis calcd (%) for C47H36Cl2OP2Pt: C 59.75,H 3.84; found: C
60.00,H 3.89.
Synthesis of [Pt
(h3-C3H5)(DPP-Xantphos)]PF6 (5): Allyl(tri-n-butyltin)
N
(33 mL,1 equiv) and AgOTf (27 mg,1 equiv) were added to a solution of
the complex 4 (100 mg,0.106 mmol) in THF (20 mL) at room tempera-
ture. The mixture was stirred for 4 h and completion was checked by
31P NMR analysis. The solvent was removed under vacuum,dichlorome-
thane (5 mL) was added,and after removal of the silver salts by centrifu-
gation,the filtrate was concentrated. The resulting solid was washed five
times with dichloromethane/hexanes (1:10,10 mL) to remove ClS nBu3
General procedure for allylation of amines: Complex
5 (21 mg for
1 mol%,10.5 mg for 0.5 mol%,2.1 mg for 0.1 mol%) was placed in a
Schlenk tube with 65 mg of NH4PF6 (20 mol%) and toluene/acetonitrile
(1:1,2 mL). Allyl alcohol (136 mL,2 mmol) and amine (4 mmol) were
then added. The mixture was stirred at the given temperature and for the
indicated time (see Table 2). The reaction mixture was then concentrated,
water was added (3 mL),and the product was extracted with diethyl
ether (3 mL). After conventional workup,the organic layer was purified
by flash column chromatography to yield the allyl amines listed in
Table 2. The NMR data obtained for the coupling products are in agree-
ment with the corresponding literature (allylbenzylamine,[62] allylbutyl-
salts. The corresponding solid was dried under vacuum to yield yellow 5
1
(104 mg,92%).
31P{1H} NMR (CD2Cl2): d=À0.4 (s+sat, JPt,P
=
4080 Hz), À146.2 (sept, 1JP,F =752 Hz); 1H NMR (CD2Cl2): d=1.59 (s,
3H; C
N
A
(m,2H; H allyl),4.95 (vsept, ꢀJ=57 Hz,1H; H allyl),7.05–7.34 (m,16H;
Ph),7.37–7.66 ppm (m,14H; H Ph); 13C NMR (CD2Cl2): d=26.7 (C-
(CH3)2),38.3
(CH3)2),72.3 (m +sat, ꢀ2JC,P =24 Hz, 1JPt,C =85 Hz;
CH2allyl),110.2 (d, 1JP,C =51 Hz; CxantheneP),115.7 (CH allyl),126.5 (vt, ꢀJ=
amine,[63] allylhexylamine,[64] allyl-1-phenylethylamine,[65] allylbenzylme-
H
thylamine,[66] allylmorpholine,[67] allylbenzylisopropylamine,[68] allylaniline
and all the coupling products between amines and cinnamyl alcohol[37]).
A
(
C
ACHTREUNG
8 Hz; CPh),126.9 (d,
JP,C =4 Hz; CPh),127.0 (d, JP,C =4,4 Hz; CPh),129.0
(CPh),129.7 (C Ph),129.8 (C Ph),129.9 (C Ph),133.0 (d, 2JC,P =7.9 Hz; Cipso-Ph),
133.1 (d, 2JC,P =7.1 Hz; Cipso-Ph),134.7 (vt, ꢀJ=14.6 Hz; Cb-phosphole),135.1
(vt, ꢀJ=14.1 Hz; Cb-phosphole),137.7 (C Ph),148.0 (AXX ’, ꢀJ=40.6 Hz;
Acknowledgement
C
a-phosphole),148.7 (AXX ’, ꢀJ=40.6 Hz; Ca-phosphole),158.1 ppm (vt, ꢀJ=
7.1 Hz; CO); elemental analysis calcd (%) for C50H41F6OP3Pt: C 56.66,H
3.90; found: C 56.17,H 3.91.
The CNRS,the Ecole Polytechnique,and the IDRIS (for computer time,
project no. 081616) are thanked for supporting this work.
Synthesis of [Pt(h2-C3H5NH2
amine (21 mL,10 equiv) was added to a solution of 5 (20 mg,0.019 mmol)
A
ACHTREUNG
in [D8]toluene (1 mL) at room temperature. After few seconds,the mix-
ture became red and homogeneous,and 31P NMR spectroscopy con-
firmed complete formation of the 6. 31P{1H} NMR ([D8]toluene): d=14.1
[1] R. Bencheikh,R. Chaabouni,A. Laurent,P. Mison,A. Nafti,
thesis 1983,685.
Syn-
(d+sat, 1JPt,P =3280, 2JP =18.8 Hz; PA),16.4 (d +sat, 1JPt,P =3554,
APB
2JP =18.8 Hz; PB), À146.2 (sept, 1JP,F =752 Hz); partial 13C NMR
[4] J. Tsuji, Transition Metal Reagents and Catalysis,Wiley-VCH,Wein-
APB
heim, 2000.
([D8]toluene): d=26.1 (CHCH2NH2
A
(
CH2NH2
A
[5] B. M. Trost,C. Lee, Catalytic Asymmetric Synthesis,Wiley-VCH,
50.9 (NH
A
ACHTREUNG
2
Synthesis of [Pt(h2-C3H5OH)(DPP-Xantphos)] (7): Allyl alcohol (72 mL,
10 equiv) and NaBH4 (20 mg,5 equiv,in 1 mL of water) were added to a
solution of complex 4 (100 mg,0.106 mmol) in THF (20 mL) at room
temperature. The solution,which became homogeneous and turned red,
was stirred for few minutes until 31P NMR spectroscopy indicated com-
plete conversion. The mixture was concentrated under vacuum,and the
residue was dissolved in dichloromethane and centrifuged in order to
remove insoluble salts. The resultant solution was evaporated and the
solid was washed with dichloromethane/hexanes (1:10),filtered off and
New York, 2000.
[7] H. Bricout,J. F. Carpentier,A. Mortreux, J. Mol. Catal. A 1998, 136,
243.
[8] L. Usui,S. Schmidt,M. Keller,B. Breit,
[9] Y. Yokoyama,H. Hikawa,M. Mitsuhashi,A. Uyama,Y. Murakami,
[10] Y. Yokoyama,H. Hikawa,M. Mitsuhashi,A. Uyama,Y. Hiroki,Y.
[13] F. Ozawa,H. Okamoto,S. Kawagishi,S. Yamamoto,T. Minami,M.
dried to yield desired orange 7 (93 mg,94%). 31P{1H} NMR (CD2Cl2):
2
d=14.2 (d+sat, 2JP,P =16.6 Hz, 1JPt,P =3220 Hz),15.6 (d +sat, JP,P
=
1
1
16.6 Hz, JPt,P =3554 Hz); H NMR (CD2Cl2): d=0.71–0.74 (m,1H; OH),
1.55 (s,6H; C
(CH3)2),1.68 (d,1H, 3JH,H =8.9 Hz; H2C=CHCH2OH),1.81
A
[14] G. Mora,B. Deschamps,S. van Zutphen,X. F. Le Goff,L. Ricard,P.
[15] O. Piechaczyk,M. Doux,L. Ricard,P. le Floch,
(d,1H, 3JH,H =5.1 Hz; H2C=CHCH2OH),2.88–3.11 (vqt,1H, ꢀJ=59 Hz;
CHCH2OH),3.51–3.72 (m,2H; C H2OH),6.95–7.19 (m,16H; H Ph),7.21
(dd,4H, 3JHP =20.7 Hz; Hb-phosphole),7.43 (d,2H, 3JH,H =6.9 Hz; HPh),7.72
(d,6H, 3JH,H =7.1 Hz; HPh),7.80 ppm (d,2H,
13C NMR (CD2Cl2): d=27.0 (C
(CH3)2),37.9 ( C
1JC,Pt =174 Hz;
H2C=CHCH2OH),62.7 (s +sat,
CHCH2OH),65.4 (s +sat, 2JC,Pt =33.5 Hz; CH2OH),116.7 (d, JPC
3JH,H =7.1 Hz; HPh);
(CH3)2),42.2 (s +sat,
1JC,Pt =238 Hz;
[16] C. Thoumazet,H. Grutzmacher,B. Deschamps,L. Ricard,P. le
[17] C. Dubs,T. Yamamoto,A. Inagaki,M. Akita,
A
ACHTREUNG
=
=
=
=
31 Hz),117.2 (d,
7.6 Hz),127.9 (d,
J
J
P,C =34 Hz),124.6 (d,
P,C =3.4 Hz),129.2 (d,
J
P,C =4.7 Hz),127.0 (d, JP,C
[18] Y. Yamashita,A. Gopalarathnam,J. F. Hartwig, J. Am. Chem. Soc.
2007, 129,7508.
2
J
P,C =4.3 Hz),131.3 (d, JP,C
12.0 Hz; Cb-phosphole),131.8 (d, 2JP,C =12.2 Hz; Cb-phosphole),132.1 (d, JP,C
2
12.1 Hz; Cb-phosphole),132.3 (d, 2JP,C =9.8 Hz; Cb-phosphole),135.4–135.8 (m,
CxantheneP),135.9 (d, 2JP,C =14.9 Hz; Cipso-Ph),137.2 (d, 2JP,C =3.3 Hz; Cipso-Ph),
10056
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA,Weinheim
Chem. Eur. J. 2008, 14,10047 – 10057