A R T I C L E S
Zalubovskis et al.
129.6, 128.7, 128.6, 128.5, 128.4, 127.9, 127.7, 127.3, 126.8, 126.7,
126.3, 105.4, 77.6, 61.4, 59.2, 55.3, 53.4, 27.6.
different configurational preferences of the ligand provide an
explanation for the contrasting behavior of different types of
allylic substrates in Pd-catalyzed allylic alkylations employing
P,N-ligands which are electronically dissymmetric and sterically
exhibit C2 or Cs-symmetry (pseudo-C2- and pseudo-Cs-sym-
metric, respectively). The complexes containing the configu-
rationally flexible ligand provide examples of a new class of
self-adaptable catalytic systems.
[1,2-Bis-[(R)-4,5-dihydro-3H-dinaphtho[1,2-c:2′,1′-e]azepino]-
ethane] η3-1,3-Diphenylpropenyl Palladium Hexafluorophosphate
(16). This complex was prepared from Ra,Ra-N,N-ligand 11 (11.1 mg,
18 µmol) and bis[(η3-1,3-diphenylpropenyl)palladium chloride] (6.0 mg,
9 µmol), by the same procedure as that used for the preparation of 14
(stirring at 50 °C for 20 min). Recrystallization from CH2Cl2/hexane
gave 16 (12 mg, 62%); mp 227-229 °C; [R]25D -397.0 (c 0.125, CH2-
1
Cl2); H NMR (500 MHz, CDCl3) δ 8.30-8.25 (m, 2H), 8.22-8.16
Experimental Section
(m, 3H), 8.08-7.84 (m, 4H), 7.83-7.73 (m, 1H), 7.71-7.63 (m, 3H),
7.60-7.46 (m, 4H), 7.41-7.18 (m, 8H), 7.08-6.89 (m, 5H), 6.76-
6.68 (m, 2H), 6.46-6.33 (m, 2H), 6.01 (dd, J ) 13.2, 10.1 Hz, 1H),
5.46 (d, J ) 13.2 Hz, 1H), 5.28 (d, J ) 12.3 Hz, 1H), 4.20 (d, J )
11.9 Hz, 1H), 3.83 (d, J ) 13.7 Hz, 1H), 3.81 (d, J ) 10.1 Hz, 1H),
3.11-3.01 (m, 1H), 2.82 (d, J ) 13.8 Hz, 1H), 2.58-2.36 (m, 4H),
2.17 (d, J ) 11.9 Hz, 1H), 1.50 (d, J ) 12.9 Hz, 1H), 1.37 (d, J )
13.0 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 137.6, 137.2, 136.5,
134.7, 134.2, 134.1, 133.9, 133.2, 133.1, 132.9, 132.3, 132.2, 131.7,
131.5, 130.9, 130.6, 130.0, 129.5, 129.2, 129.1, 129.0, 128.7, 128.6,
128.4, 128.3, 128.2, 128.1, 128.0, 127.9, 127.7, 127.4, 126.9, 126.8,
126.6, 126.5, 126.3, 126.1, 125.8, 125.7, 102.2, 92.2, 67.2, 60.1, 59.7,
59.6, 58.6, 57.8, 56.1.
[1-[(R)-4,5-Dihydro-3H-dinaphtho[1,2-c:2′,1′-e]azepino]-2-[(S)-
4,5-dihydro-3H-dinaphtho[1,2-c:2′,1′-e]azepino]ethane] η3-1,3-Diphe-
nylpropenyl Palladium Hexafluorophosphate (17). This complex was
prepared from Ra,Sa-N,N-ligand 12 (11.1 mg, 18 µmol) according to
the procedure used for the preparation of 16 (stirring at 50 °C for 5
min). Recrystallization from CH2Cl2/hexane gave 17 (10 mg, 52%);
mp 225-226 °C; 1H NMR (500 MHz, CDCl3) δ 8.29 (d, J ) 8.0 Hz,
2H), 8.16 (d, J ) 8.2 Hz, 2H), 8.00 (d, J ) 8.2 Hz, 2H), 7.93-7.88
(m, 5H), 7.72-7.54 (m, 10H), 7.52-7.16 (m, 11H), 6.67-6.61 (m,
2H), 6.13 (t, J ) 11.7 Hz, 1H), 4.59 (d, J ) 11.8 Hz, 2H), 4.42 (d, J
) 11.9 Hz, 2H), 3.69 (d, J ) 14.3 Hz, 2H), 3.56-3.45 (m, 2H), 3.13
(d, J ) 12.0 Hz, 2H), 2.56 (d, J ) 14.0 Hz, 2H), 2.55-2.47 (m, 2H);
13C NMR (125 MHz, CD2Cl2) δ 137.1, 135.8, 135.1, 134.7, 134.0,
132.6, 131.8, 131.5, 130.5, 130.1, 129.4, 129.0, 128.9, 128.7, 128.6,
128.5, 128.3, 128.2, 128.0, 127.6, 127.1, 126.9, 126.7, 126.6, 109.5,
78.1, 78.0, 77.7, 77.5, 62.3, 58.7, 55.9.
[1,2-Bis-[4,5-dihydro-3H-dibenzo[c-e]azepino]ethane] η3-Cyclo-
hexenyl Palladium Hexafluorophosphate (18). This complex was
prepared from ligand 13 (46.7 mg, 112 µmol) by the same procedure
as that used for the preparation of 14 (stirring at 50 °C for 30 min).
Recrystallization from CH2Cl2/hexane gave 18 (26 mg, 31%); mp 192-
193 °C; 1H NMR (500 MHz, CDCl3) δ 7.67 (d, J ) 7.5 Hz, 2H), 7.63-
7.44 (m, 14H), 5.60 (t, J ) 6.6 Hz, 1H), 4.45 (d, J ) 13.7 Hz, 2H),
4.25 (app t, J ) 5.8 Hz, 2H), 4.08 (d, J ) 11.9 Hz, 2H), 3.95 (d, J )
13.7 Hz, 2H), 3.63 (m, 2H), 3.22 (d, J ) 11.9 Hz, 2H), 2.88 (m, 2H),
1.62-1.55 (m, 1H), 1.51-1.42 (m, 2H), 1.37-1.29 (m, 2H), 0.85-
0.76 (m, 1H); 13C NMR (125 MHz, CD2Cl2) δ 142.0, 141.3, 132.9,
131.2, 130.9, 130.3, 130.1, 129.0, 128.9, 128.6, 128.5, 106.3, 77.4,
61.5, 60.0, 56.0, 28.2, 20.4.
[1,2-Bis-[4,5-dihydro-3H-dibenzo[c-e]azepino]ethane] η3-1,3-
Diphenylpropenyl Palladium Hexafluorophosphate (19). This com-
plex was prepared from ligand 13 (31.2 mg, 75 µmol) according to the
procedure used for the preparation of 16 (stirring at 50 °C for 20 min).
Recrystallization from CH2Cl2/hexane gave 19 (25 mg, 39%); mp 224-
225 °C; 1H NMR (500 MHz, CDCl3) δ 7.78 (d, J ) 6.8 Hz, 2H), 7.58-
7.46 (m, 7H), 7.45-7.33 (m, 8H), 7.09-6.88 (m, 9H), 6.18 (t, J )
11.8 Hz, 1H), 4.85 (d, J ) 11.8 Hz, 2H), 4.19-4.02 (m, 2H), 3.40 (d,
J ) 13.0 Hz, 2H), 3.29-3.19 (m, 2H), 3.12-3.03 (m, 2H), 3.01-2.87
(m, 4H); 13C NMR (125 MHz, CD2Cl2) δ 141.7, 141.3, 136.1, 132.8,
132.1, 131.5, 130.5, 130.1, 130.0, 129.7, 129.0, 128.9, 128.7, 128.6,
128.1, 105.1, 79.6, 60.7, 60.3, 57.9.
General. All air-sensitive reactions were performed in oven-dried
glassware under nitrogen. CH2Cl2 was taken from a Glass-contour
1
solvent-dispensing system. H and 13C NMR spectra were run at 500
and 125 MHz, respectively, and chemical shifts are reported relative
to CHCl3. Compounds 11,5 12,2 bis[(η3-cyclohexenyl)palladium chlo-
ride]7 and bis[(η3-1,3-diphenylpropenyl)palladium chloride]8 were
prepared according to published methods.
1,2-Bis-[(R)-4,5-dihydro-3H-dinaphtho[1,2-c:2′,1′-e]azepino]-
ethane (13). A mixture of 2,2′-bis(bromomethyl)-1,1′-biphenyl (200
mg, 0.59 mmol), 1,2-diaminoethane (20.6 µL, 0.31 mmol), and
triethylamine (2.25 mL) in PhMe (1.5 mL) was heated in SmithProcess
Vial in a microwave cavity for 10 min at 160 °C. H2O (10 mL) and
saturated aqueous NaHCO3 (3 mL) were added, and the mixture was
extracted with CH2Cl2 (2 × 20 mL). The solvent was evaporated, and
the crude product was purified by column chromatography on silica
gel (column 2 cm × 12 cm) (CH2Cl2 (100 mL) and then CH2Cl2/MeOH
95:5) to give 13 (61 mg, 50%). 1H NMR and 13C NMR are in agreement
with literature data.6
[1,2-Bis-[(R)-4,5-dihydro-3H-dinaphtho[1,2-c:2′,1′-e]azepino]-
ethane] η3-Cyclohexenyl Palladium Hexafluorophosphate (14). CH2-
Cl2 (15 mL) was added to a mixture of Ra,Ra-N,N-ligand 11 (66 mg,
107 µmol), bis[(η3-cyclohexenyl)palladium chloride] (24.8 mg, 53
µmol), and AgPF6 (27.1 mg, 107 µmol) in a sealed flask at -78 °C,
and the mixture was degassed. The temperature was allowed to increase
to 50 °C, and the mixture was stirred at that temperature under N2 for
10 min. After rapid cooling to room temperature the mixture was filtered
through a Celite plug and concentrated. After recrystallization of the
crude product from CH2Cl2/hexane, complex 14 (72 mg, 71%) was
obtained; mp 232-233 °C; [R]25D -440.0 (c 0.10, CH2Cl2); 1H NMR
(500 MHz, CD2Cl2) δ 8.07-7.96 (m, 4H), 7.85-7.75 (m, 5H), 7.61
(d, J ) 8.3 Hz, 1H), 7.54-7.47 (m, 3H), 7.42-7.33 (m, 4H), 7.31-
7.19 (m, 3H), 7.17-7.09 (m, 2H), 7.03-6.98 (m, 2H), 5.63 (app t, J
) 6.6 Hz, 1H), 4.41 (d, J ) 12.3 Hz, 1H), 4.34 (d, J ) 11.8 Hz, 1H),
4.29-4.24 (m, 2H), 4.09 (s, 2H), 4.00 (d, J ) 13.5 Hz, 1H), 3.87 (m,
1H), 3.23-3.15 (m, 1H), 3.04-2.93 (m, 2H), 2.84 (d, J ) 11.7 Hz,
1H), 2.30-2.23 (m, 2H), 1.74-1.64 (m, 2H), 1.55-1.45 (m, 2H), 1.27-
1.18 (m, 1H), 0.96-0.86 (m, 1H); 13C NMR (125 MHz, CD2Cl2) δ
137.4, 137.0, 136.3, 136.2, 135.6, 135.5, 134.7, 134.3, 134.2, 134.1,
132.3, 132.0, 131.9, 131.6, 131.5, 130.3, 129.9, 129.7, 129.6, 129.5,
129.3, 129.2, 129.0, 128.9, 128.8, 128.7, 128.4, 128.1, 128.0, 127.8,
127.6, 127.5, 127.4, 127.2, 127.1, 127.0, 126.9, 126.8, 107.0, 78.3,
78.2, 62.4, 61.6, 61.3, 58.7, 57.8, 55.8, 29.7, 28.1, 20.9.
[1-[(R)-4,5-Dihydro-3H-dinaphtho[1,2-c:2′,1′-e]azepino]-2-[(S)-
4,5-dihydro-3H-dinaphtho[1,2-c:2′,1′-e]azepino]ethane] η3-Cyclo-
hexenyl Palladium Hexafluorophosphate (15). This complex was
prepared from Ra,Sa-N,N-ligand 12 (57.6 mg, 93 µmol) by the same
procedure as that used for the preparation of 14 (stirring at 50 °C for
30 min). Recrystallization from CH2Cl2/hexane gave 15 (64 mg, 72%);
1
mp 217-218 °C; H NMR (500 MHz, CDCl3) δ 8.01-7.85 (m, 8H),
7.75 (d, J ) 8.3 Hz, 2H), 7.63 (d, J ) 8.2 Hz, 2H), 7.49-7.36 (m,
6H), 7.33-7.15 (m, 6H), 5.52 (t, J ) 6.4 Hz, 1H), 4.57 (d, J ) 13.6
Hz, 2H), 4.05 (d, J ) 11.7 Hz, 2H), 3.88 (d, J ) 13.9 Hz, 2H), 3.83
(m, 2H), 3.56 (m, 2H), 3.10 (d, J ) 11.5 Hz, 2H), 2.58 (m, 2H), 1.42-
1.33 (m, 1H), 1.23-1.04 (m, 4H), 0.61-0.50 (m, 1H); 13C NMR (125
MHz, CDCl3) δ 137.1, 135.1, 133.8, 133.6, 131.6, 131.5, 131.1, 130.2,
TRISPHAT and BINPHAT Complexes. Salts [18][rac-20], [18]-
[∆-20], [18][∆-21], [19][rac-20], [19][∆-20], and [19][∆-21] were
9
1854 J. AM. CHEM. SOC. VOL. 130, NO. 6, 2008