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Y. Alvarez-Casao et al. / Tetrahedron xxx (2015) 1e7
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4.8. Pyridineehydrazone (L9)
Mp¼122e124 ꢁC. [
a
]
D
ꢀ229.2 (c 0.80, CHCl3). 1H NMR (300 MHz,
CDCl3):
d 8.34 (s, 2H), 7.84 (s, 1H), 7.68e7.25 (m, 13H), 7.07 (s, 1H),
Following the general procedure, flash chromatography
5.25 (d, 2H, J¼6.7 Hz), 2.61e2.55 (m, 2H), 1.94e1.84 (m, 2H). 13C
(EtOAc:n-hexane 1:20, 1% Et3N) gave L9 (342 mg, 85%) as a yellow-
NMR (75 MHz, CDCl3): d 157.1, 153.1, 142.8, 141.7, 136.8, 132.3 (q,
20
orange foam. [
CDCl3):
a
]
ꢀ259.5 (c 0.54, CHCl3). 1H NMR (300 MHz,
JCeF¼34.0 Hz), 131.4, 128.7, 127.1, 127.0, 126.9, 126.3, 122.3 (q,
D
d
7.87 (m, 2H), 7.62e7.22 (m, 16H), 7.09 (s, 1H), 5.23 (d, 2H,
JCeF¼272.0 Hz),122.1,118.4,117.9, 65.4, 31.6. HRMS (CI) m/z calcd for
J¼6.8 Hz), 2.59e2.52 (m, 2H), 1.91e1.81 (m, 2H). 13C NMR (75 MHz,
C
30H24N3F6 540.1874 (Mþþ1), found 540.1882.
CDCl3):
d 156.5, 156.4, 143.0, 139.8, 136.3, 132.3, 128.6, 128.5, 128.4,
126.9, 126.8, 126.2, 117.9, 116.8, 65.2, 31.4. HRMS (CI) m/z calcd for
28H25N3 403.2048, found 403.2061.
4.14. Pyridineehydrazone (L15)
C
Following the general procedure, flash chromatography
4.9. Pyridineehydrazone (L10)
(EtOAc:n-hexane 1:8, 1% Et3N) gave L15 (334 mg, 75%) as a white
20
solid. Mp¼137e138 ꢁC. [
a
]
D
ꢀ260.9 (c 0.90, CHCl3). 1H NMR
Following the general procedure, flash chromatography (Et2O:n-
(300 MHz, CDCl3): d 7.52e7.23 (m, 15H), 7.07 (s, 1H), 6.82 (d, 1H,
hexane 1:8/1:4, 1% Et3N) gave L10 (314 mg, 73%) as a white solid.
J¼8.1 Hz), 5.94 (s, 2H), 5.23 (d, 2H, J¼6.7 Hz), 2.58e2.53 (m, 2H),
20
Mp¼112e113 ꢁC. [
a]
ꢀ310.2 (c 0.83, CHCl3). 1H NMR (300 MHz,
1.87e1.85 (m, 2H). 13C NMR (125 MHz, CDCl3):
d
156.2, 155.9, 148.0,
D
CDCl3):
d
7.82 (d, 2H, J¼8.8 Hz), 7.56e7.42 (m, 2H), 7.40e7.19 (m,
143.0, 136.3, 134.2, 132.2, 128.6, 128.5, 126.9, 126.2, 120.8, 117.3,
116.3, 108.3, 107.4, 101.1, 65.2, 31.4. HRMS (CI) m/z calcd for
11H), 7.10 (s, 1H), 6.93 (d, 2H, J¼8.8 Hz), 5.23 (d, 2H, J¼6.7 Hz), 3.82
(s, 3H), 2.70e2.45 (m, 2H), 1.95e1.75 (m, 2H). 13C NMR (75 MHz,
C29H25N3O2 447.1947, found 447.1949.
CDCl3):
d 160.1, 156.3, 156.1, 143.0, 136.3, 132.5, 132.4, 128.5, 128.1,
126.8, 126.2, 117.2, 116.1, 113.9, 65.2, 55.3, 31.5. HRMS (CI) m/z calcd
4.15. General procedure for the synthesis of palladium com-
plexes C1eC4
for C29H28N3O 434.2232 (Mþþ1), found 434.2234.
4.10. Pyridineehydrazone (L11)
Under an argon atmosphere, [Pd(CH3CN)2Cl2] (75 mg, 0.3 mmol)
was added to solution of L (0.3 mmol) in dry CH2Cl2 (5 mL). The
reaction mixture was stirred at room temperature for 2 h, con-
centrated to dryness, washed with dry Et2O and dried in vacuo to
give the palladium dichloride complex. Yields and characterization
data for compounds C1eC4 are as follows:
Following the general procedure, flash chromatography (tolue-
ne:n-hexane 1:1/2:1, 1% Et3N) gave L11 (334 mg, 79%) as a yellow
20
solid. Mp¼115e117 ꢁC. [
a]
ꢀ58.8 (c 0.90, CHCl3). 1H NMR
D
(300 MHz, CDCl3):
d
7.88e7.81 (m, 2H), 7.54 (dd, 1H, J¼7.9, 0.9 Hz),
7.47 (t, 1H, J¼7.9 Hz), 7.38e7.32 (m, 4H), 7.30 (dd, 1H, J¼7.9, 0.9 Hz),
7.28e7.21 (m, 6H), 7.12e7.04 (m, 3H), 5.24 (d, J¼7.0 Hz), 2.62e2.49
4.16. Palladium complex C1
(m, 2H), 1.97e1.78 (m, 2H). 13C NMR (75 MHz, CDCl3):
d 163.3 (q,
J¼249.0 Hz), 156.4, 155.3, 142.9, 136.4, 132.0, 128.7, 128.6, 126.9 (q,
J¼7.8 Hz), 126.6, 126.2, 117.5, 116.7, 115.4 (q, J¼23.2 Hz), 65.3, 31.6
HRMS (CI) m/z calcd for C28H25N3F (Mþþ1) 422.2028, found
422.2033.
Following the general procedure, C1 was obtained as a red solid
(112 mg, 74%). X-ray quality crystals were grown by slow diffusion
of AcOEt into a solution of C1 in CH2Cl2. Mp¼160e162 ꢁC (dec).
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[
a
]
¼235.4ꢁ (c 0.57, CHCl3). 1H NMR (500 MHz, C2D6CO):
d 8.89 (d,
D
1H, J¼5.4 Hz), 7.95 (t, 1H, J¼7.4 Hz), 7.73e7.18 (m, 10H), 6.91e6.74
4.11. Pyridineehydrazone (L12)
(m 2H), 5.48e5.33 (m, 1H), 2.78e2.53 (m, 2H), 2.11e1.90 (m, 2H).
13C NMR (125 MHz, CDCl3):
d 156.9, 150.65, 147.8, 143.9, 141.3,
Following the general procedure, flash chromatography (tolu-
139.5, 130.0, 129.4, 129.0, 128.9, 128.4, 127.6, 125.1, 125.0, 69.1, 66.0,
35.0, 32.6. HRMS m/z calcd for C22H20N3Pd 432.0674. Found
432.0678.
ene, 1% Et3N) gave L12 (352 mg, 88%) as a yellow foam. [
a
]
20 ꢀ330.9
D
(c 0.80, CHCl3). 1H NMR (300 MHz, CDCl3):
d
7.58 (dd, 1H, J¼8.1,
2.0 Hz), 7.50 (t, 1H, J¼7.4 Hz), 7.36e7.33 (m, 4H), 7.26e7.24 (m, 6H),
7.14e7.10 (m, 1H), 7.06e7.00 (m, 3H), 7.03 (s, 1H), 6.88 (dd, 1H,
J¼7.4, 1.1 Hz), 5.22 (d, 2H, J¼7.0 Hz), 2.60e2.51 (m, 2H), 1.99 (s, 6H),
4.17. Palladium complex C2
1.90e1.84 (m, 2H). 13C NMR (125 MHz, CDCl3):
d
158.6, 156.5, 142.8,
Following the general procedure, C2 was obtained as an orange
140.6, 135.9, 135.8, 132.2, 128.5, 127.6, 127.5, 126.8, 126.3, 121.5,
116.1, 65.2, 31.4, 20.2. HRMS (CI) m/z calcd for C30H30N3 432.2440
(Mþþ1), found 432.2435.
solid (151 mg, 94%). X-ray quality crystals were grown by slow
diffusion of n-hexane into
a solution of C2 in CH2Cl2.
20
Mp¼234e235 ꢁC (dec). [
a
]
D
¼177.5ꢁ (c 0.60, CHCl3). 1H NMR
(300 MHz, CDCl3):
d
8.42 (d, 1H, J¼6.8 Hz), 7.58e7.17 (m, 11H),
4.12. Pyridineehydrazone (L13)
6.93e6.81 (m, 2H), 6.64 (d, 1H, J¼2.5 Hz), 6.53 (dd, 1H, J¼6.8,
2.5 Hz), 5.06e4.86 (m, 1H), 3.83 (s, 3H), 2.78e2.54 (m, 2H),
2.17e1.92 (m, 2H). 13C NMR (75 MHz, CDCl3): 167.8, 156.7, 151.2,
144.4, 142.3, 137.5, 129.6, 128.8, 128.5, 128.0, 127.8, 126.3, 110.0,
108.6, 68.4, 65.5, 56.5, 34.1, 31.2. HRMS m/z calcd for
Following the general procedure, flash chromatography
(EtOAc:n-hexano 1:20, 1% Et3N) gave L13 (437 mg, 95%) as
20
a yellow foam. [
CDCl3):
a
]
ꢀ256.8 (c 0.62, CHCl3). 1H NMR (300 MHz,
D
d
7.81e7.77 (m, 2H), 7.57e7.23 (m, 15H), 7.11 (s, 1H), 5.25
C23H23ON3ClPd 498.0557. Found 498.0559.
(dd, 2H, J¼6.8, 1.2 Hz), 2.59e2.51 (m, 2H), 1.91e1.80 (m, 2H), 1.33
(s, 9H). 13C NMR (125 MHz, CDCl3):
d
156.6, 156.3, 151.5, 143.0,
4.18. Palladium complex C3
137.1, 136.2, 132.5, 128.6, 128.5, 126.8, 126.6, 126.2, 125.5, 116.4,
65.2, 34.6, 31.4, 31.2. HRMS (CI) m/z calcd for C32H33N3 459.2674,
found 459.2662.
Following the general procedure, C3 was obtained as an orange
solid (194 mg, 91%). X-ray quality crystals were grown by slow
diffusion of n-hexane into
a solution of C3 in CH2Cl2.
4.13. Pyridineehydrazone (L14)
Mp¼143e145 ꢁC. 1H NMR (300 MHz, CDCl3):
d 7.91 (br s, 1H),
7.85e7.74 (m, 3H), 7.64e7.35 (m, 11H), 7.58e7.17 (m, 11H),
7.29e6.92 (m, 1H), 7.11 (d, 1H, J¼7.9 Hz), 6.91 (s, 1H), 6.65e6.50 (m,
Following the general procedure, flash chromatography (tolue-
ne:n-hexane 1:2, 1% Et3N) gave L14 (486 mg, 90%) as a yellow solid.
1H), 5.04e4.80 (m, 1H), 2.80e2.53 (m, 2H), 2.25e1.96 (m, 2H). 13
C
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