A. Gogoll et al.
FULL PAPER
stirred at 08C for 1 h. The mixture was filtered and the solid was washed
with water followed by acetone. The resulting crystals were recrystallized
from carbon tetrachloride giving slightly yellow crystals that were dried
under vacuum, (1.84 g, 50%). M.p. 1038C (Lit: 103 ± 103.58C); 1H NMR
(400 MHz, CDCl3, 258C): d 3.67 (dd, J(H,H) 10.1, 4.1 Hz, 4H; CH2I),
3.18 (dd, J(H,H) 10.1, 6.2 Hz, 4H; CH2I), 1.51 (t, J(H,H) 6.7 Hz, 2H;
CH2), 1.38 (m, 2H; CH); 13C NMR (100.6 MHz, CDCl3, 258C): d 39.2,
1H; H5), 2.01 (m, 1H; H1), 1.90 (d, J(H,H) 6.9 Hz, 3H; CH311), 1.75 (d,
J(H,H) 6.9 Hz, 3H; CH313), 1.27 (d, J(H,H) 6.8 Hz, 3H; CH3butenyl),
1.08(m, 2H; CH29); [(2R,3S)-3 ´ (S,S)-1], 1H NMR (400 MHz, [D6]acetone,
ꢀ308C): d 7.2 ± 7.6 (m, 10H; Ph), 5.9 ± 6.0 (m, 1H; H2butenyl), 4.85 (m, 1H;
H3butenyl), 4.71 (q, J(H,H) 6.9 Hz, 1H; H10), 4.50 (q, J(H,H) 6.9 Hz,
1H; H12), 3.83 (m, 1H; H4eq), 3.73 (m, 1H; H1syn), 3.52 (m, 1H; H1anti),
3.47 (m, 1H; H6eq), 3.45 (m, 1H; H8eq), 3.23 (m, 1H; H2eq), 3.05 (m, 1H;
H4ax), 2.88 (m, 1H; H8ax), 2.42 (m, 1H; H6ax), 2.23 (m, 1H; H2ax), 2.16 (m,
1H; H5), 2.00 (m, 1H; H1), 1.92 (d, J(H,H) 6.9 Hz, 3H; CH311), 1.77 (d,
J(H,H) 6.9 Hz, 3H; CH313), 1.42 (d, J(H,H) 6.8 Hz, 3H; CH3butenyl),
1.11 (m, 2H; CH29).
37.8, 13.0; IR(KBr) nÄ 1560, 1381, 916, 722 cmꢀ1
.
(S,S)-3,7-Bis(1'-phenylethyl)-3,7-diazabicyclo[3.3.1]nonane
Compound 9 (1.8 g, 3 mmol) and (S)-1-phenylethyl amine [(S)-10] were
mixed in toluene (25 mL) and refluxed for 60 h under nitrogen
([(S,S)-1]):
a
trans-Bis[(4-acetoxy-(1,2,3-h3)-cyclohexenyl)palladium chloride]Ðchloro-
dimer of 4: This compound was prepared from cyclohexadiene.[14]
atmosphere. After cooling, the reaction mixture was extracted with aq.
NaOH (10%). The aqueous phase was re-extracted with toluene, and the
solvent of the combined organic phases was removed under reduced
pressure. The resulting oil was purified by bulb-to-bulb distillation followed
by column chromatography (pentane/diethyl ether/triethyl amine 9:9:2).
Removal of solvents under reduced pressure yielded 1 as a clear oil (0.38 g,
38%).[6a] 1H NMR (400 MHz, CDCl3, 258C): d 7.50 (m, 4H; Phortho), 7.32
(m, 4H; Phmeta), 7.23 (tt, J(H,H) 7.3, 1.4 Hz, 2H; Phpara), 3.25 (q, J(H,H)
6.7 Hz, 2H; H10), 2.93 (dd, J(H,H) 10.5, 2.7 Hz, 2H; H2,6eq), 2.72 (dd,
J(H,H) 10.5, 2.7 Hz, 2H; CH4,8eq), 2.32 (dd, J(H,H) 10.5, 3.9 Hz, 2H;
H2,6ax), 2.22 (dd, J(H,H) 10.5, 3.9 Hz, 2H; H4,8ax), 1.84 (m, 2H; H1, H5),
1.48 (t, J(H,H) 3.3 Hz, 2H; H9), 1.34 (d, J(H,H) 6.7 Hz, CH311);
13C NMR (100.6 MHz, CDCl3, 258C): d 146.5, 128.0, 127.6, 126.3, 65.4,
56.4, 54.2, 31.2, 30.1, 20.8; IR (CDCl3 solution) nÄ 3010, 2748, 2248, 1600,
[(S,S)-3,7-Bis(1'-phenylethyl)-3,7-diazabicyclo[3.3.1]nonane]{trans-{[4-
acetoxy-(1,2,3-h3)-cyclohexenyl]palladium}
trifluoromethanesulfonate}
([4 ´ (S,S)-1]): The chlorodimer of 4; 14.1 mg, 25 mmol) and silver trifluoro-
methanesulfonate (14.2 mg, 55 mmol) were added to chloroform (3 mL).
After 10 min of stirring at room temperature, the solution was centrifuged
until all the silver chloride was removed from the solution. This solution
was then mixed with (S,S)-1 (16.7 mg, 50 mmol) dissolved in chloroform
(1 mL). After 5 min of stirring, the solvent amount was reduced to
approximately 1 mL. Diethyl ether was added to initiate precipitation of
the complex, followed by storage of the mixture at ꢀ208C over night.
(20 mg, 54%). Further crystallizations of this mixture of diastereomeric
complexes yielded [(R)-4 ´ (S,S)-1] in its pure form, (8 mg, 22%). 1H NMR
(400 MHz, CDCl3, 258C): d 7.50 ± 7.35 (m, 10H; Ph), 6.21 (dd, J(H,H)
6.1 Hz, 6.1, 1H; H2allyl), 5.01 (dd, J(H,H) 6.6, 2.1 Hz, 1H; H4allyl), 4.79 (q,
J(H,H) 6.6 Hz, 1H; H12), 4.66 (q, J(H,H) 6.6 Hz, 1H; H10) 4.55 (m,
1H; H1allyl), 4.55 (m, 1H; H3allyl), 3.74 (d, J(H,H) 12.8 Hz, 1H; H8eq), 3.60
(d, J(H,H) 12.8 Hz, 1H; H2eq), 3.47 (d, J(H,H) 12.8 Hz, 1H; H4eq), 3.43
(d, J(H,H) 12.8 Hz, 1H; H6eq), 3.23 (d, J(H,H) 12.8 Hz, 1H; H8ax), 2.84
(d, J(H,H) 12.8 Hz, 1H; H4ax), 2.59 (d, J(H,H) 12.8 Hz, 1H; H2ax), 2.44
(d, J(H,H) 12.8 Hz, 1H; H6ax), 2.26 (s, 1H; H1 in 1), 2.17 (s, 1H; H5 in 1),
2.07 (s, 3H; OAc), 2.02 (m, 1H; H5eqallyl), 2.06 (m, 1H; H6axallyl), 1.87 (m,
1H; H6eqallyl), 1.81 (d, J(H,H) 6.6 Hz, 3H; CH313), 1.74 (d, J(H,H)
6.6 Hz, 3H; CH311), 1.34 (d, J(H,H) 13.8 Hz, 1H; H9), 1.26 (d, J(H,H)
13.8 Hz, 1H; H9), 1.28 (m, 1H, H5axallyl); IR (KBr) nÄ 3031, 1726, 1602,
1490, 1450 cmꢀ1
.
(R,R)-3,7-Bis(1'-phenylethyl)-3,7-diazabicyclo[3.3.1]nonane ([(R,R)-1]):
This compound was prepared according to the procedure for the
preparation of (S,S)-1, but with (R)-1-phenylethyl amine [(R)-10].
Bis[(1,2,3-h3-propenyl)palladium chloride]Ðchlorodimer of 2: This com-
pound was prepared according to literature procedures.[28]
[(S,S)-3,7-Bis(1'-phenylethyl)-3,7-diazabicyclo[3.3.1]nonane)-[(1,2,3-h3-
propenyl)palladium] trifluoromethanesulfonate] ([2 ´ (S,S)-1]): This com-
pound was prepared from the chlorodimer of 2 and (S,S)-1. 1H NMR
(400 MHz, CDCl3, ꢀ408C): d 7.37 ± 7.31 (m, 10H; Ph), 6.13 (m, 1H; H2),
4.50 (q, J(H,H) 6.4 Hz, 1H; H12), 4.43 (q, J(H,H) 6.7 Hz, 1H; H10),
3.90 (m, 1H; H4eq), 3.89 (m, 1H; H1'syn), 3.77 (d, J(H,H) 13.3 Hz, 1H;
H1'anti), 3.73 (m, 1H; H6eq), 3.55 (d, J(H,H) 6.6 Hz, 1H; H1syn), 3.35 (d,
J(H,H) 11.6 Hz, 1H; H1anti), 3.34 (m, 1H; H8eq), 3.21 (m, 1H; H2eq), 2.89
(m, 1H; H4ax), 2.73 (m, 1H; H8ax), 2.33 (m, 1H; H6ax), 2.24 (m, 1H; H2ax),
2.14 (m, 1H; H5,1), 2.00 (m, 1H; H5,1), 1.84 (d, J(H,H) 6.7 Hz, 3H;
CH311), 1.71 (d, J(H,H) 6.4 Hz, 3H; CH313), 1.16 (m, 2H; CH29).
1555 cmꢀ1
.
[(S)-4 ´ (S,S)-1] (in a 1:1 mixture with [(R)-4 ´ (S,S)-1]): 1H NMR (400 MHz,
CDCl3, 258C): d 7.50 ± 7.30 (m, 10H; Ph), 6.17 (dd, J(H,H) 6.6, 6.6 Hz,
1H; H2allyl), 5.13 (dd, J(H,H) 6.6, 2.1 Hz, 1H; H4allyl), 4.78 (m, 1H;
H1allyl), 4.77 (q, J(H,H) 6.6 Hz, 1H; H10), 4.38 (q, J(H,H) 6.6 Hz, 1H;
H12), 4.05 (dd, J(H,H) 6.6, 2.1, 1H; H3allyl), 3.78 (d, J(H,H) 12.8 Hz,
1H; H8eq), 3.61 (d, J(H,H) 12.8 Hz, 1H; H2eq), 3.48 (d, J(H,H) 12.8 Hz,
1H; H6eq), 3.44 (d, J(H,H) 12.8 Hz, 1H; H4eq), 3.24 (d, J(H,H) 12.8 Hz,
1H; H8ax), 2.76 (d, J(H,H) 12.8 Hz, 1H; H4ax), 3.60 (d, J(H,H) 12.8 Hz,
1H; H2ax), 2.46 (d, J(H,H) 12.8 Hz, 1H; H6ax), 2.22 (s, 1H; H1 in 1), 2.22
(m, 1H; H5eqallyl), 2.03 (s, 3H; OAc), 1.73 (d, J(H,H) 6.6 Hz, 3H; CH311),
1.50 (d, J(H,H) 6.6 Hz, 3H; CH313), 1.40 (m, 1H; H5axallyl), 1.34 (d,
J(H,H) 13.8 Hz, 1H; H9), 1.22 (d, J(H,H) 13.8 Hz, 1H; H9) (protons
Bis[(1,2,3-h3-butenyl)palladium chloride]Ðchlorodimer of 3:[29] PdCl2
(1.45 g, 8.2 mmol) and NaCl (1.0 g, 17.1 mmol) were suspended in a
mixture of methanol (25 mL) and water (3 mL). The suspension was heated
until the solution became dark red and all the salts were dissolved.
3-Chlorobut-1-ene (5.0 mL, 50 mmol) was added in one portion. Carbon
monoxide was passed through the solution, and a yellow solid started to
precipitate. After 10 min, water (100 mL) was added until the salts were
dissolved. The solution was extracted with chloroform (3 Â 100 mL). The
organic phase was dried over Na2SO4 and evaporated. The crude product
was recrystallized from acetone/pentane (1:1) yielding a yellow solid (3 ´
Cl)2 (1.29 g, 80%). 1H NMR (400 MHz, CDCl3, 258C): d 5.29 (dddd,
J(H,H) 0.7, 6.8, 11.2, 11.9 Hz, 1H; H2), 3.91 (mqd, J(H,H) 0.9, 6.3,
11.2 Hz, 1H; H3), 3.89 (dd, J(H,H) 0.9, 6.8 Hz, 1H; H1syn), 2.82 (ddd,
J(H,H) 0.9, 0.9, 11.9 Hz, 1H; H1anti), 1.34 (dd, J(H,H) 0.7, 6.3 Hz, 3H;
CH3).
[(S,S)-3,7-Bis(1'-phenylethyl)-3,7-diazabicyclo[3.3.1]nonane)(1,2,3-h3)-bu-
tenyl palladium tetrafluoroborate] ([3 ´ (S,S)-1]): The chlorodimer of 3
(19.6 mg, 100 mmol of monomer) and AgBF4 (19.5 mg, 100 mmol) were
dissolved in [D6]acetone. After 10 min of stirring at room temperature
under argon, silver chloride was removed by centrifugation. This solution
was then added to ligand (S,S)-1 (33.5 mg, 100 mmol), stirred for 10 min
under argon, and subjected to NMR investigation. Equimolar mixture of
two isomers: [(2S,3S)-3 ´ (S,S)-1]: 1H NMR (400 MHz, [D6]acetone,
ꢀ308C): d 7.2 ± 7.6 (m, 10H; Ph), 5.8 ± 6.0 (m, 1H; H2butenyl), 4.61 (q,
J(H,H) 6.9 Hz, 3H; H12), 4.26 (q, J(H,H) 6.9 Hz, 3H; H10), 4.03 (m,
1H; H1syn), 3.90 (m, 1H; H4eq), 3.80 (m, 1H; H1anti), 3.69 (m, 1H; H3butenyl),
3.65 (m, 1H; H6eq), 3.41 (m, 1H; H8eq), 3.19 (m, 1H; H2eq), 3.08 (m, 1H;
H4ax), 2.85 (m, 1H; H8ax), 2.38 (m, 1H; H6ax), 2.28 (m, 1H; H2ax) 2.14 (m,
on C6 and H5 in 1 obscured); IR (KBr) nÄ 3031, 1726, 1602, 1555 cmꢀ1
.
Bis[2-methylene-6,6-dimethylbicyclo[3.1.1]hept-(2,3,10-h3)-enyl)palladi-
um chloride]Ðchlorodimer of (S)-5: This compound was prepared from b-
pinene.[16]
[(S,S)-3,7-Bis(1'-phenylethyl)-3,7-diazabicyclo[3.3.1]nonane]{[2-methyl-
ene-6,6-dimethylbicyclo[3.1.1]hept-(2,3,10-h3)-enyl]palladium trifluoro-
methanesulfonate} ([(S)-5 ´ (S,S)-1]): The chlorodimer of (S)-5 (13.9 mg,
25 mmol) and silver trifluoromethane sulfonate (14.2 mg, 55 mmol) were
added to chloroform (3 mL). After 10 min of stirring at room temperature,
the solution was centrifuged until all the silver chloride was removed from
the solution. This solution was then mixed with (S,S)-1 (16.7 mg, 50 mmol)
dissolved in chloroform (1 mL). After 5 min of stirring, the solvent amount
was reduced to approximately 1 mL. Diethyl ether was added to initiate
precipitation of the complex, followed by storage of the mixture at ꢀ208C
1
over night; this yielded a colorless oil (17 mg, 59%). H NMR (400 MHz,
CDCl3, 258C): d 7.40 ± 7.30 (m,10H; Ph), 4.46 (q, J(H,H) 6.6 Hz, 1H;
H10), 4.20 (s, 1H; H10b), 4.19 (d, J(H,H) 11.8 Hz, 1H; H4eq), 4.14 (q,
J(H,H) 6.6 Hz, 1H; H12), 3.92 (d, J(H,H) 11.8 Hz, 1H; H6eq), 3.90 (brs,
1H, H3), 3.65 (s, 1H; H10a), 3.23 (d, J(H,H) 11.8 Hz, H8eq), 2.98 (dd
J(H,H) 11.8, 3.5 Hz, 1H; H4ax), 2.86 (d, J(H,H) 11.8 Hz, 1H; H2eq),
2.85 (m, 1H; H7b), 2.82 (d, J(H,H) 11.8 Hz, 1H; H8ax), 2.51 (m, 1H;
402
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0702-0402 $ 17.50+.50/0
Chem. Eur. J. 2001, 7, No. 2