M. ꢀngeles Chꢁvez et al.
FULL PAPERS
2H, 2 CHMe2), 4.95 (brm, 2H, =CH, COD), 6.14 (brm, 2H, with Et2O (3ꢅ3 mL), dissolved in CH2Cl2, and filtered
=CH, COD), 6.72 (brm, 1H, H arom), 7.15 (s, 2H, H
arom), 7.38 (m, 2H, H arom), 7.47 (s, 2H, H arom), 7.53
(m, 1H, H arom); 31P{1H} NMR (CD2Cl2, 162 MHz): d=
through Celite. Evaporation of the solvent produced com-
pound 15 as an orange oil. H NMR (CD2Cl2, 400 MHz): d=
1.21 (dd, JH,P =15.2 Hz, JH,H =6.8 Hz, 3H, CHMe2), 1.27 (s,
9H, CMe3), 1.41 (m, 9H, MeC=+2CHMe2), 1.50 (s, 9H,
CMe3), 1.68 (dd, JH,P =16.4 Hz, JH,H =6.0 Hz, 3H, CHMe2),
1.77 (s, 3H, Ar-Me), 1.86 (s, 3H, Ar-Me), 2.30 (s, 3H, Ar-
Me), 2.34 (s, 3H, Ar-Me), 2.73 (brm, 1H, CHMe2), 3.15
1
17.2 (dd, JP, P =45 Hz, JP,Rh =137 Hz, PC), 132.9 (dd, JP, P
=
45 Hz,
J
P,Rh =270 Hz, PO); 13C{1H} NMR (CD2Cl2,
101 MHz): d=18.5 (s, 2CH2 COD), 19.9 (s, 2CH2 COD),
26.5 (d, JC,P =26 Hz, 2 CHMe2), 30.2 (d, JC,P =19 Hz, 2
CHMe2), 31.4 (s, CMe3), 34.8 (s, CMe3), 35.4 (s, CMe3), 96.9
(brm, =CH COD), 123.2 (s, 2Cq arom), 125.3 (s, 2CH),
126.2 (s, 2Cq arom), 127.5 (s, 2CH), 130.5 (s, CH arom),
131.8 (s, CH arom), 133.2 (s, CH arom), 139.8 (s, 2Cq arom),
145.1 (s, Cq arom), 148.6 (s, CH arom), 154.9 (s, Cq arom);
HR-MS (FAB): m/z=859.3857, calcd. for C48H70O3P2Rh
[MÀBF4]+: 859.3855.
(brm, 1H, CHMe2), 3.63 (d, JH,P =11.2 Hz, 3H, P
ACHTUNGRTEN(NUNG OMe)2),
3.69 [d, JH,P =10.8 Hz, 3H, P(OMe)2], 4.78 (br s, 1H, =CH),
AHCTUNGTRENNUNG
6.67 (brm, 1H, H arom), 7.22 (s, 1H, H arom), 7.37 (s, 1H,
H arom), 7.40–7.65 (m, 5H, 5 H arom), 7.78 (t, JH,H =7.3 Hz,
1H,
31P{1H} NMR (CD2Cl2, 162 MHz): d=13.6 (dd, JP,Rh
140 Hz, JP, P =63 Hz, PC), 14.9 [s, P(O)(OMe)2], 132.0 (dd,
P, Rh =262 Hz,
P, P =62 Hz, PO); 13C{1H} NMR (CD2Cl2,
H arom), 8.01 (d, JH,H =7.6 Hz, 2H, 2H arom);
=
AHCTUNGTRENNUNG
J
J
101 MHz): d=16.6 (s, Ar-Me), 16.7 (s, Ar-Me), 17.4 (s,
CHMe2), 17.7 (s, CHMe2), 19.8 (s, CHMe2), 20.2 (s,
CHMe2), 20.3 (s, Ar-Me), 20.5 (s, Ar-Me), 22.0 (br s, MeC=
{RhACHTUNGTRENNUNG(COD)[(R)-2b]}BF4 (4b)
Over a solution of [RhACHTNUTRGNE(UGN COD)2]BF4 (0.036 g, 0.09 mmol) in
CH2Cl2 (10 mL), was added dropwise (R)-2b (0.049 g,
0.10 mmol) dissolved in CH2Cl2 (10 mL). The resulting solu-
tion was stirred for 0.5 h, concentrated up to a fourth of the
volume and filtered. Subsequent slow addition of Et2O
(40 mL) precipitated 4b as a yellow solid which was filtered
), 23.5 (d,
CHMe2), 32.0 (s, 3CMe3), 32.2 (s, 3CMe3), 35.1 (s, CMe3),
35.4 (s, CMe3), 52.0 [br s, P(OMe)2], 52.6 [s, P(OMe)2], 58.1
JC,P =23 Hz, CHMe2), 29.9 (d, JC,P =23 Hz,
A
ACHTUNGTRENNUNG
(br d, JC,P =176 Hz, CH=), 114.5 (d, JC,P =35 Hz, Cq arom),
119.8 (br s, OCq=), 122.7 (s, CH arom), 125.7 (s, Cq arom),
126.6 (d, JC,P =4 Hz, CH arom), 129.2 (s, CH arom), 129.5 (s,
Cq arom), 129.5 (s, Cq arom), 129.7 (s, 2CH arom), 130.0 (s,
CH arom), 131.1 (s, 2CH arom), 131.7 (s, CH arom), 133.9
(s, CH arom), 135.0 (s, 2Cq arom), 135.9 (s, Cq arom), 136.5
(s, CH arom), 137.0 (s, 2Cq arom), 137.7 (Cq arom), 144.4
(d, JC,P =7 Hz, Cq arom), 144.8 (d, JC,P =14 Hz, Cq arom),
155.2 (dd, JC,P =7 Hz, JC,P =7 Hz, Cq arom), 164.2 (Cq
arom), 180.0 (br s, C=O).
1
and washed twice with Et2O; yield: 0.057 g (75%). H NMR
(CDCl3, 300 MHz): d=1.17 (dd, JH,P =9.9 Hz, JH,H =7.5 Hz,
3H, CHMe2), 1.23 (dd, JH,P =9.3 Hz, JH,H =6.9 Hz, 3H,
CHMe2), 1.32 (dd, JH,P =13.5 Hz, JH,H =6.6 Hz, 3H, CHMe2),
1.38 (s, 9H, CMe3), 1.52 (dd, JH,P =13.8 Hz, JH,H =7.2 Hz,
3H, CHMe2), 1.58 (s, 9H, CMe3), 1.70 (s, 3H, Ar-Me), 1.79
(s, 3H, Ar-Me), 1.78–2.60 (m, 12H, 4CH2 COD+PCH2 +
2CHMe2), 2.23 (s, 3H, Ar-Me), 2.27 (s, 3H, Ar-Me), 3.61
(brm, 1H, =CH COD), 4.42 (m, 1H, CHHO), 4.54 (m, 1H,
CHHO), 5.33 (brm, 1H, =CH COD), 5.66 (brm, 1H, =CH
COD); 5.72 (brm, 1H, =CH COD), 7.16 (s, 1H, H arom),
7.20 (s, 1H, H arom); 31P{1H} NMR (CDCl3, 121 MHz): d=
[Rh(1c)ACHTUNGTRNEUNG
(h6-C6H6)]BF4 (17)
Compound 3c (10 mg) was dissolved in C6H6 (0.5 mL), the
mixture was kept under H2 for 24 h, whereupon the reaction
was complete by 31P{1H} NMR. The solution was evaporated
to dryness, affording 17 as a yellow solid; yield: 8 mg (83%).
16.1 (dd, JP, Rh =137 Hz, PC), 121.1 (dd, JP, Rh =250 Hz, JP, P
=
52 Hz, PO); 13C{1H} NMR (CDCl3, 75 MHz): d=16.6 (Ar-
Me), 16.8 (Ar-Me), 18.3 (m, PCH2), 18.9 (CHMe2), 19.0
(CHMe2), 20.6 (Ar-Me), 20.7 (Ar-Me), 21.3 (d, JC,P =2 Hz,
CHMe2), 27.6 (d, JC,P =24 Hz, CHMe2), 27.9 (d, JC,P =22 Hz,
CHMe2), 29.2 (CH2 COD), 30.0 (CHMe2), 30.1 (CH2 COD),
31.1 (CH2 COD), 31.6 (CH2 COD), 31.9 (CMe3), 32.6
(CMe3), 35.0 (CMe3), 35.2 (CMe3), 65.1 (CH2O), 89.1 (dd,
1H NMR (CD2Cl2, 400 MHz): d=1,10 (dd, JH,H =6.9, JH,P
=
16.7 Hz, 6H, CHMe2), 1.32 (s, 18H, CMe3), 1.40 (s, 18H,
CMe3), 1.29 (dd, JH,H =7.0 Hz, JH,P =20.0 Hz, 6H, CHMe2),
2.45 (dd, JH,H =7.0 Hz, JH,H =14.5 Hz, 2H, CHMe2), 6.37 (s,
6H, C6H6), 7.05 (m, 2H, H arom), 7.28 (d, JH,H =2.1 Hz, 2H,
H arom), 7.48 (m, 2H, H arom), 7.58 (d, JH,H =1.8 Hz, 2H,
H arom); 31P {1H} NMR (CD2Cl2, 162 MHz): d=43.1 (dd,
J
J
C,P =7 Hz, JC,Rh =7 Hz, =CH COD), 103.0 (dd, JC,P =9 Hz,
C,Rh =7 Hz, =CH COD), 104.9 (dd, JC,P =11 Hz, JC,Rh =5 Hz,
J
P, P =55 Hz, JP, Rh =188 Hz, PC), 136 (dd, JP, P =55 Hz, JP,Rh =
=CH COD), 107.7 (d, JC,P =7 Hz, Cq arom), 109.6 (dd, JC,P
=
338 Hz, PO); 13C {1H} NMR (CD2Cl2, 101 MHz): d=18.8 (d,
J=12 Hz, CHMe3), 28.6 (d, J=27 Hz, CHMe3), 31.5 (s,
CMe3), 31.7 (s, CMe3), 35.1 (s, CMe3), 35.7 (s, CMe3), 104.0
(s, C6H6), 122.7 (s, Cq), 125.9 (s, 2CH arom), 127.6 (s, 2CH
arom), 128.6 (s, 4CH arom), 130.6 (s, 2Cq), 131.3 (s, Cq),
133.6 (s, 2Cq), 140.7 (d, JC,P =3 Hz, PCq arom), 145.2 (s, Cq
arom), 145.2 (s, Cq arom), 149.1 (s, Cq arom); MS-ESI
13 Hz, JCP =7 Hz, =CH COD), 128.4 (CH arom), 129.3 (CH
arom), 129.6 (Cq arom), 134.0 (Cq arom), 134.1 (Cq arom),
135.7 (Cq arom), 136.4 (Cq arom), 137.3 (2Cq arom), 144.7
(d, JC,P =13 Hz, OCq arom), 145.2 (OCq arom); elem. anal.
calcd. for C40H62BF4O3P2Rh·0.5CH2Cl2 (%): C 54.96, H 7.17,
found: C 55.00, H 7.11.
(CH2Cl2): m/z=829.3, [Rh(1c)ACHTUNGTRNEUNG
(h6-C6H6)]+.
{Rh[(S)-1b](6a)}BF4 (15)
A Fischer–Porter reaction vessel was charged with a solution
of [RhACHTUNGTRENNUNG(NBD)[(S)-1b]]BF4 (0.050 g, 0.06 mmol) in DME
Acknowledgements
(3 mL) and pressurized under 4 atm of H2. The reaction
mixture was stirred for 5 h, and then depressurized. To the
resulting solution, 6a (0.021 g, 0.08 mmol) was added and
the mixture obtained was stirred for 30 min. The solution
was evaporated to dryness and the resulting solid washed
Financial support (Feder contribution) from the Spanish
MICINN (grants GSD2007-11867 and Consoilder Ingenio
CSD 2007-0006), Junta de Andalucia (2008/FQM-3830) and
2792
ꢄ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 2775 – 2794