Organic Syntheses via Transition Metal Complexes
Organometallics, Vol. 17, No. 6, 1998 1201
°C), which on isomerization affords compound 7b (633 mg,
98%, Rf ) 0.6 in pentane/dichloromethane, 2:1, violet crystals,
mp 123 °C).
4,8-Bis(2-eth oxy-1,1,1,1,1-pen tacar bon yl-1-tu n gstaeth en -
2-yl)-1-eth oxy-2,5-dim eth yl-3,7-diph en ylazabicyclo[4.2.0]-
octa -3,7-d ien e (3c) a n d 3-(2-Eth oxy-1,1,1,1,1-p en ta ca r bo-
n yl-1-t u n gst a et h en -2-yl)-5-(2-et h oxy-4-p h en yl-1,1,1,1,1-
p en ta ca r bon yl-1-tu n gsta -1,3-bu ta d ien -4-yl)-6-eth oxy-1,4-
d im eth yl-1,4-d ih yd r op yr id in e (7c). N-Methyl crotonamide
(5c) (129 mg, 1.30 mmol) is successively reacted with triethyl-
oxonium tetrafluoroborate (285 mg, 1.50 mmol), pentacarbo-
nyl(1-ethoxy-3-phenyl-2-propyn-1-ylidene)tungsten (1) (964
mg, 2.00 mmol), and triethylamine (202 mg, 2.00 mmol) as
described above to give compound 3c (424 mg, 39%, Rf ) 0.6
in pentane/dichloromethane, 2:1, red crystals), which on
isomerization affords compound 7c (400 mg, 94%, Rf ) 0.6 in
pentane/dichloromethane, 2:1, violet crystals).
3b. 1H NMR (CDCl3, 600 MHz): δ 7.52-7.30 (15 H, m, 3
Ph), 5.19 (1 H, s, dynamically broadened, 5-H), 5.00 and 4.84
(1 H each, dynamically broadened signals, 2′′-OCH2), 4.00 and
3.85 (1 H each, dynamically broadened signals, 2′-OCH2), 3.90
(1 H, s, 6-H), 2.90 and 2.70 (1 H each, dynamically broadened
signals, 1-OCH2), 2.82 (1 H, sept, NCH), 1.70 (3 H, t broad,
CH3, 1-OEt), 1.20 and 0.84 [3 H each, d each, C(CH3)2], 1.00
and 0.74 (3 H each, t each, CH3 each, 2′-OEt and 2′′-OEt). 13C
NMR (CDCl3, 150 MHz): δ 315.2 and 313.2 (Cq each, WdC
each), 204.1 and 201.7 [trans-CO, W(CO)5], 197.8 and 196.6
[cis-CO, W(CO)5], 152.3 [Cq, CdC(N), C3], 144.8, 142.6, 142.0,
141.3, 134.7, and 130.8 (Cq each, C4, C7, C8, 3 i-C Ph), 129.0-
127.6 (CH each, 3 Ph), 98.8 (Cq, C1), 79.0 (2′′-OCH2), 78.0 (2′-
OCH2 broad), 61.4 (1-OCH2), 56.2 (CH, C5), 45.3 (CHMe2), 45.0
(CH, C6), 21.7 and 21.0 [N(CH3)2]; 14.9, 14.7, and 14.4 (3
CH2CH3). IR (hexane), cm-1: 2060.9 (20), 1973.6 (5), 1938.6
(100) [ν(CtO)]. Anal. Calcd for C46H39NO13W2 (1181.5): C,
46.76; H, 3.33; N, 1.19. Found: C, 46.53; H, 3.36; N, 1.20.
7b. 1H NMR (C6D6): δ 7.79 (1 H, s, 3′-H), 7.36 and 7.31 (2
H each, “d” each, o-H Ph each), 7.26 and 7.08 (2 H each, “t”
each, m-H Ph each), 7.12 and 7.00 (1 H each, “t” each, p-H Ph
each), 7.14-7.04 (5 H, dynamically broadened signal of 4′-Ph),
5.00 (1 H, s, 4-H), 4.18 (2 H, m, 2′-OCH2), 4.16 (1 H, sept,
CHN), 4.03 (2 H, m, 2′′-OCH2), 3.65 and 3.35 (1 H each, m
each, diastereotopic 6-OCH2), 0.95 and 0.85 [3 H each, dias-
tereotopic C(CH3)2], 0.81, 0.75, and 0.49 (3 H each, CH2CH3
each). 13C NMR (C6D6): δ 320.4 and 302.8 (Cq each, WdC
each), 204.3 and 202.4 [trans-CO, W(CO)5], 197.0 and 198.4
[cis-CO, W(CO)5], 176.2 (Cq, C6), 158.2 [Cq, CdC(N), C2], 144.5
(CH, C3′), 144.3, 140.9, 140.3, 135.7, and 133.3 (Cq each, C3,
C4′, and 3 i-C Ph), 129.6-127.2 (CH each, 3 Ph), 103.2 (Cq,
C5), 79.4 and 78.2 (CH2 each, 2′′-OCH2 and 2′-OCH2), 69.9 (6-
OCH2), 52.6 (HCN), 46.8 (CH, C4), 23.0 and 21.5 [diaste-
reotopic C(CH3)2]; 14.6, 14.2, and 13.6 (3 CH2CH3). IR
(hexane), cm-1: 2064.1 (20, broad), 1981.0 (5), 1938.6 (100,
broad) [ν(CtO)]. Anal. Calcd for C46H39NO13W2: C, 46.76; H,
3.33; N, 1.19. Found: C, 46.60; H, 3.09; N, 1.08.
3c. 1H NMR (C6D6): δ 7.25-7.00 (10 H, m, 2 Ph), 4.45 (2
H, q, 2′′-OCH2), 3.95 (3 H, m, 2′-OCH2 and 5-H), 3.30 (1 H, s,
6-H), 3.20 (2 H, m, 1-OCH2), 2.29 (3 H, s, NCH3), 1.29 (3 H, d,
3J ) 7 Hz, 5-CH3), 1.18, 1.12, and 0.56 (3 H each, t each,
CH2CH3 each). 13C NMR (C6D6): δ 322.8 and 318.8 (Cq each,
WdC each), 204.2 and 202.9 [trans-CO, W(CO)5], 198.9 and
197.3 [cis-CO, W(CO)5], 157.4 (Cq, CdC(N), C3], 138.4, 138.2,
138.1, 131.4, and 130.0 (Cq each; C4, C7, C8, 2 i-C Ph); 129.9,
129.0, 130.3, 129.6, 129.3, and 129.1 (1:1:2:1:2:1, CH each, 2
Ph), 93.1 (Cq, C1), 78.4 (2′′-OCH2 broad), 77.4 (2′-OCH2), 61.7
(1-OCH2), 53.9 (CH, C5), 46.6 (CH, C6), 33.4 (NCH3), 20.5 (5-
CH3), 14.9, 14.5, and 14.2 (3 CH2CH3). IR (hexane), cm-1
:
2070.6 (20), 2060.7 (20), 1982.7 (5), 1954.4 (80), 1932.1 (100)
[ν(CtO)]. Anal. Calcd for C39H33NO13W2 (1091.4): C, 42.92;
H, 3.05; N, 1.28. Found: C, 42.67; H, 3.33; N, 1.36.
7c. 1H NMR (C6D6): δ 7.86 (1 H, s, 3′-H), 7.15-6.90 (10 H,
m, 2 Ph), 4.30-4.20 (4 H, m, 2′-OCH2 and 2′′-OCH2), 4.16 (1
H, q, 4-H), 3.60 and 3.35 (1 H each, m each, diastereotopic
6-OCH2), 2.35 (3 H, s, NCH3), 1.35 (3 H, d, 4-CH3), 1.00, 0.90,
and 0.51 (3 H each, CH2CH3 each). 13C NMR (C6D6): δ 319.1
and 298.3 (Cq each, WdC each), 204.4 and 202.9 [trans-CO,
W(CO)5], 198.9 and 196.0 [cis-CO, W(CO)5], 169.1 (Cq, C6),
158.2 [Cq, CdC(N), C2], 145.3 (CH, C3′), 142.4, 142.1, 134.0,
and 132.6 (Cq each, C3, C4′ and 2 i-C Ph), 129.5-127.4 (CH
each, 3 Ph), 103.5 (Cq, C5), 81.6 and 78.2 (CH2 each, 2′′-OCH2
and 2′-OCH2), 68.5 (6-OCH2), 42.7 (CH, C4), 31.4 (NCH3), 22.7
X-ray crystal structure analysis of 7b: formula C46H39
-
(4-CH3), 15.2, 14.4, and 13.7 (3 CH2CH3). IR (hexane), cm-1
:
NO13W2, M ) 1181.47, 0.40 × 0.30 × 0.20 mm, a ) 11.936(1)
Å, b ) 12.798(1) Å, c ) 15.314(1) Å, R ) 93.91(1)°, â ) 94.00-
(1)°, γ ) 97.24(1)°, V ) 2308.0(3) Å3, Fcalc ) 1.700 g cm-3, µ )
50.43 cm-1, empirical absorption correction via æ scan data
(0.829 e C e 0.999), Z ) 2, triclinic, space group P1h (No. 2), λ
) 0.710 73 Å, T ) 223 K, ω/2θ scans, 9808 reflections collected
(-h, (k, (l), [(sin θ)/λ] ) 0.62 Å-1, 9341 independent and 6744
observed reflections [I g 2σ(I)], 564 refined parameters, R1 )
0.032, wR2 ) 0.073, maximum residual electron density 1.89
(-1.99) e Å-3 close to W, hydrogens calculated and riding. All
data sets were collected with an Enraf Nonius MACH3
diffractometer. Programs used: data reduction, MolEN; struc-
ture solution, SHELXS-86; structure refinement, SHELXL-
93; graphics, DIAMOND.
2070.2 (20), 2060.3 (20), 1983.4 (5), 1958.5 (80), 1932.1 (100)
[ν(CtO)]. Anal. Calcd for C39H33NO13W2 (1091.4): C, 42.92;
H, 3.05; N, 1.28. Found: C, 42.76; H, 3.16; N, 1.26.
Ack n ow led gm en t . This investigation was sup-
ported by the Stiftung Volkswagenwerk and by the
Fonds der Chemischen Industrie.
Su p p or tin g In for m a tion Ava ila ble: Tables of positional
and displacement parameters, bond distances and angles, and
hydrogen coordinates for compounds 3a and 7b (21 pages).
Ordering information is given on any current masthead page.
OM9708586