t
3
1
(
2
(
.01 (s, 3H, O
m, 1H, OCH(CH
-H), 3.21 (m, 1H, 6-H), 4.42 (m, 1H, 5-H), 4.60 (m, 1H, 4-H), 4.95
dd, J = 3.4, 8.6 Hz, 1H, 3-H), 5.16 (m, 1H, C CHCHCHC ),
), 5.50 (d, J = 3.6 Hz, 1H, 1-H),
), 7.78–6.83 (m, 18H, aromatic).
, 100.6 MHz, ppm): d 19.5 (OCH(CH3)2),
2
C(CH
3
), 1.75–1.25 (m, 39H, O
2
C(CH
3
)
2
, Bu), 2.70
[Pd(g -C15
H
13)(L8a)]PF
6
(12). By using general procedures,
3
3
)
2
), 2.76 (m, 1H, 6-H), 3.12 (d, J = 3.6 Hz, 1H,
complex 12 was synthesised starting from [PdCl(h -C15
(0.025 mmol) and diphosphite ligand L8a (0.05 mmol). Complex
12 was characterised by NMR analysis, and precipitated as a pale
yellow solid in 82% yield (63 mg, 0.041 mmol). HRMS (ESI+)
calculated for (C93
1548.8699.
H
13)]
2
6
H
5
6
H
5
5
.36 (m, 1H, C
.62 (m, 1H, C
6
H
5
CHCHCHC
CHCHCHC
Cl
6
H
5
+
6
6
H
5
6
H
5
H
135
O
8
P
2
Pd ): m/z = 1548.8696, found m/z =
1
3
1
C { H} NMR (CD
2
2
2
3
5
9
1
0.6 (OCH(CH
0.2 ( Bu), 35.2–33.4 ( Bu), 66.5 (C-6), 70.5 (OCH(CH
3
)
2
), 25.0 (O
2
C(CH
3
)
2
), 25.1 (O
2
C(CH
3
)
2
), 31.4–
1
Isomer 12A. H NMR (CD
2
Cl
2
, 400 MHz, ppm): d 0.60 (d, J =
t
t
3 2
)
), 74.6 (C-
t
5
.6 Hz, 3H, 6-H), 0.92 (m, 3H, OC16
33), 2.87 (m, 2H, 2-H, OC16 33), 2.99 (m, 1H, OC16
dd, J = 4.4, 10.0 Hz, 1H, 1-H), 3.68 (dd, J = 4.6, 9.8 Hz, 1H, 1-H),
H
33), 1.74–1.25 (m, 64H, Bu,
), 75.8 (C-4), 79.8 (C-3), 82.7 (C-2), 83.6 (C
7.6 (C CHCHCHC ), 104.2 (C-1), 111.3 (O
11.9 (C CHCHCHC
Cl , 161.97 MHz, ppm): d 131.3 (d, J = 202.8 Hz, 1P),
6
H
5
CHCHCHC
6
H
5
),
OC16
H
H
H33), 3.61
6
H
5
6
H
5
2
C(CH
3
1
)
2
),
(
3
1
6
H
5
6
H
5
), 148.8–121.6 (aromatics). P { H}
3
4
1
7
.77 (dd, J = 3.9, 9.6 Hz, 1H, 4-H), 4.38 (m, 1H, 5-H), 5.00 (dd, J =
.4, 8.8 Hz, 1H, 3-H), 5.16 (m, 1H, C CHCHCHC ), 5.38 (m,
H, C CHCHCHC ), 6.64 (m, 1H, C CHCHCHC ),
Cl , 100.6
33), 26.2 (C-6), 32.7–
33), 73.0(C-1),
CHCHCHC ),
CHCHCHC ), 150.3–
Cl , 161.97 MHz, ppm): d
NMR (CD
1
2
2
6
H
5
6
H
5
33.6 (d, J = 199.6 Hz, 1P).
6
H
5
6
H
5
6
H
5
6
H
5
1
3
1
.77–6.84 (m, 18H, aromatic). C { H} NMR (CD
2
2
3
[
Pd(g -C15
H
13)(L7a)]PF (11). By using general procedures,
complex 11 was synthesised starting from [PdCl(h -C15
0.025 mmol) and diphosphite ligand L7a (0.05 mmol). Complex
1 was characterised by NMR analysis, and precipitated as a pale
6
MHz, ppm): d 14.4 (OC16
H
33), 23.2 (OC16
H
3
H
13)]
2
t
t
2
7
9
1
1
9.6 ( Bu, OC16
H
33), 36.7–34.7 ( Bu), 70.7 (OC16
H
(
1
5.2 (C-5), 82.4(C-3), 83.6 (C-2), 84.8 (C
9.2 (C CHCHCHC ), 112.9 (C
6
H
5
6
H
5
6
H
5
6
1
H
5
6
H
5
6
H
5
yellow solid in 70% yield (51 mg, 0.035 mmol). HRMS (ESI+)
3
1
23.2 (aromatics). P { H} NMR (CD
2
2
+
calculated for (C86
479.7310.
H
119
O
10
P Pd ): m/z = 1479.7308, found m/z =
2
30.6 (d, J = 205.8 Hz, 1P), 133.0 (d, J = 207.0 Hz, 1P).
1
1
Isomer 12B. H NMR (CD
5.6 Hz, 3H, 6-H), 0.92 (m, 3H, OC16
33), 2.87 (m, 2H, 2-H, OC16 33), 2.99 (m, 1H, OC16
(dd, J = 4.4, 10.0 Hz, 1H, 1-H), 3.68 (dd, J = 4.6, 9.8 Hz, 1H, 1-H),
3.77 (dd, J = 3.9, 9.6 Hz, 1H, 4-H), 4.50 (m, 1H, 5-H), 4.88 (dd, J =
2
Cl
2
, 400 MHz, ppm): d 0.78 (d, J =
1
t
Isomer 11A. H NMR (CD
t, J = 6.8 Hz, 3H, CH CH CH
C(CH ,CH
2
Cl
2
, 400 MHz, ppm): d 0.68
), 0.99 (s, 3H, O C(CH ),
, Bu), 2.86 (d, J =
H
33), 1.74–1.25 (m, 64H, Bu,
(
2
2
3
2
3
OC16
H
H
H
33), 3.61
t
1
3
4
8
.75–1.05 (m, 43H, O
2
3
)
2
2
CH
2
CH
3
.6 Hz, 1H, 2-H), 3.19 (m, 1H, 6-H), 3.39 (m, 1H, 6-H),
.52 (m, 1H, 5-H), 4.58 (m, 1H, 4-H), 4.77 (dd, J = 2.8,
3.6, 8.8 Hz, 1H, 3-H), 5.16 (m, 1H, C
6
H
5
CHCHCHC
CHCHCHC
Cl , 100.6
33), 26.4 (C-6), 32.7–
33), 72.8 (C-
CHCHCHC ),
CHCHCHC ), 150.3–
Cl , 161.97 MHz, ppm): d
6
H
5
), 5.38 (m,
.0 Hz, 1H, 3-H), 5.00 (m, 1H, C
CHCHCHC ), 5.41 (d, J = 3.6 Hz, 1H,1-
H), 6.58 (m, 1H, C CHCHCHC ), 7.76–6.82 (m, 18H,
Cl , 100.6 MHz, ppm): d 14.8
), 17.4 (OC(CH CH CH CH ), 24.4
), 26.9 (O C(CH
CH CH CH
6
H
5
CHCHCHC
6
H
5
), 5.36
1H, C CHCHCHC ), 6.64 (m, 1H, C
6
H
5
6
H
5
6
H
5
6
H
5
),
1
3
1
(
m, 1H, C
6
H
5
6
H
5
7.77–6.84 (m, 18H, aromatic). C { H} NMR (CD
2
2
6
H
5
6
H
5
MHz, ppm): d 14.4 (OC16
H
33), 23.2 (OC16
H
1
3
1
t
t
aromatic). C { H} NMR (CD
2
2
29.6 ( Bu, OC16
H
33), 36.7–34.7 ( Bu), 70.9 (OC16
H
(
(
OC(CH
OC(CH
3
)
)
2
CH
CH
2
CH
CH
2
CH
CH
3
3
)
2
2
2
3
1), 75.2 (C-5), 82.4(C-3), 84.5 (C-2), 85.3 (C
98.8 (C CHCHCHC ), 112.9 (C
6
H
5
6
H
5
H
5
6
1
H
5
6
H
5
6
H
5
3
2
2
2
3
), 25.8 (O
2
C(CH
3
)
2
2
3
)
2
3
),
),
6
t
t
31
3
6
4
2.9–29.6 ( Bu), 36.7–34.8 ( Bu), 43.7 (OC(CH
1.2 (C-6), 75.0 (OC(CH
), 81.0 (C-3), 83.8 (C-2), 84.8 (C
3
)
2
2
2
123.2 (aromatics). P { H} NMR (CD
2
2
131.1 (d, J = 204.8 Hz, 1P), 133.3 (d, J = 204.7 Hz, 1P).
3
)
2
CH
2
CH
2
CH
3
), 76.0 (C-5), 77.2 (C-
CHCHCHC ), 99.8
), 105.8 (C-1), 113.4 (O C(CH ), 113.7
), 150.2–123.2 (aromatics). P { H} NMR
6
H
5
6
H
3 2
)
5
(
(
(
(
C
C
CD
6
H
H
5
5
CHCHCHC
CHCHCHC
6
H
H
5
5
2
Acknowledgements
3
1
1
6
6
We thank the Spanish Ministerio de Educaci o´ n y Ciencia
(CTQ2007-62288/BQU, CTQ2005-03124, CTQ2010-15835, Con-
solider Ingenio 2010, CSD2006-0003, FPU program/AP2005-
1263 to A. Gual, 2008PGIR/07 to O. P a` mies and 2008PGIR/08
and ICREA Academia award to M. Di e´ guez), the Catalan
Government (2009SGR116 and the Distinction for Research
Promotion 2003 award to C. Claver) for financial support.
2
Cl
2
, 161.97 MHz, ppm): d 131.3 (d, J = 202.8 Hz, 1P), 133.5
d, J = 202.6 Hz, 1P).
1
Isomer 11B. H NMR (CD
2
Cl
2
, 400 MHz, ppm): d 0.77
), 0.99 (s, 3H, O
(
t, J = 6.2 Hz, 3H, CH
2
CH
2
CH
3
2
C(CH ),
3
t
1
1
1
.75–1.05 (m, 43H, O
2
C(CH
3
)
2
,CH
2
CH
2
CH
3
,
Bu), 2.91 (m,
H, H-2), 3.62 (m, 1H, 6-H), 3.70 (m, 1H, 6-H), 4.42 (m,
H, 5-H), 4.61 (m, 1H, 4-H), 4.68 (m, 1H, 3-H), 5.14 (m, 1H,
C
6
H
5
CHCHCHC
6
H
5
), 5.29 (m, 1H, C
6
H
5
CHCHCHC
CHCHCHC
.76–6.82 (m, 18H, aromatic). C { H} NMR (CD
00.6 MHz, ppm): 14.8 (OC(CH CH CH CH ), 17.4
CH CH CH (OC(CH CH CH ),
C(CH ), 26.9 (O
6
H
5
), 5.46
),
Cl
Notes and references
(
d, J = 4.0 Hz, 1H, 1-H), 6.58 (m, 1H, C
6
H
5
6
H
5
1
3
1
1 For reviews, see: (a) J. Tsuji, in Palladium Reagents and Catalysis,
Innovations in Organic SynthesisWiley: New York, 1995; (b) B. M. Trost
and D. L. van Vranken, Chem. Rev., 1996, 96, 395; (c) M. Johannsen
and K. A. Jorgensen, Chem. Rev., 1998, 98, 1689; (d) A. Pfaltz and M.
Lautens, in Comprehensive Asymmetric Catalysis, ed. E. N. Jacobsen, A.
Pfaltz and H. Yamamoto, Springer-Verlag, Berlin, 1999, Vol. 2, Chapter
7
1
2
2
,
d
3
)
2
2
2
3
(OC(CH
3
)
2
2
2
3
),
24.4
3
)
2
CH
2
2
3
t
25.8 (O
2
3
)
2
2
C(CH
3
)
2
), 32.9–29.6 ( Bu), 36.7–
t
34.8 ( Bu), 43.2 (OC(CH
3
)
2
CH
2
CH
2
CH ), 61.6 (C-6), 75.2
3
2
4; (e) G. Helmchen and A. Pfaltz, Acc. Chem. Res., 2000, 33, 336; (f) A.
(
(
1
1
OC(CH
C-2), 85.2 (C
3
)
2
CH
2
CH
CHCHCHC
05.4 (C-1), 112.7 (C CHCHCHC
2
CH
3
), 76.2 (C-5), 77.4 (C-4), 81.0 (C-3), 84.1
M. Masdeu-Bult o´ , M. Di e´ guez, E. Mart ´ı n and M. G o´ mez, Coord. Chem.
Rev., 2003, 242, 159; (g) B. M. Trost and M. L. Crawley, Chem. Rev.,
6
H
5
6
H
5
), 99.5 (C
), 113.2 (O
Cl
6
H
5
CHCHCHC
6
H
5
),
),
2
1
003, 103, 2921; (h) E. Mart ´ı n and M. Di e´ guez, C. R. Chim., 2007, 10,
88; (i) Z. Lu and S. Ma, Angew. Chem., Int. Ed., 2008, 47, 258.
6
H
5
6
H
5
2
C(CH )
3
2
3
1
1
50.2–123.2 (aromatics). P { H} NMR (CD
2
2
, 161.97 MHz,
2
(a) M. Di e´ guez, S. Jansat, M. Gomez, A. Ruiz, G. Muller and C. Claver,
ppm): d 132.3 (d, J = 199.5 Hz, 1P), 133.0 (d, J = 201.9 Hz, 1P).
Chem. Commun., 2001, 1132; (b) O. P a` mies, G. P. F. van Strijdonck,
This journal is © The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 2852–2860 | 2859