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(15) General Procedure for the Synthesis of α-Alkylidene-
δ-amino-δ-fluoroalkyl Oxindoles
A solution of KHMDS (0.36 mL, 1 M solution in THF) was slowly
added to a dried Scheck flask containing 3-alkenyl-2-oxindoles
2 (0.36 mmol) in THF (2.0 mL) at –78 °C under N2 atmosphere.
After stirring at –78 °C for 1 h, the mixture of 1 (0.3 mmol) and
Ti(Oi-Pr)4 (0.33 mmol) in THF (1.0 mL) was added dropwise, and
the mixture was stirred for 12 h at –78 °C. Then sat. aq NH4Cl
solution and H2O was added at –78 °C. The mixture was brought
to r.t. After 5 min, the mixture was filtered through Celite, and
the filtrate was extracted with EtOAc. The combined organic
solution was dried over MgSO4. After the removal of volatile sol-
vents under vacuum, the crude product was purified by silica
gel column chromatography to give the required product.
(16) Analytical Data for Compound 3a
Mp 60–61 °C. [α]D17.0 +187.7 (c 0.41, CHCl3). 1H NMR (400 MHz,
CDCl3): δ = 7.88 (d, J = 8.2 Hz, 1 H), 7.60 (d, J = 7.8 Hz, 1 H), 7.35
(t, J = 7.9 Hz, 1 H), 7.20 (t, J = 7.7 Hz, 1 H), 4.35 (dd, J = 24.4, 11.2
Hz, 2 H), 4.19–3.96 (m, 1 H), 2.62 (dd, J = 12.7, 3.8 Hz, 1 H), 2.43
(s, 3 H), 1.67 (s, 9 H), 1.06 (s, 9 H). 19F NMR (377 MHz, CDCl3): δ
= –74.87 (d, J = 6.5 Hz, 3 F). 13C NMR (101 MHz, CDCl3): δ =
166.5, 152.0, 149.1, 138.3, 128.9, 125.6, 125.2 (q, J = 284.8 Hz),
124.1, 123.9, 123.2, 114.6, 84.6, 57.2, 56.4 (q, J = 30.2 Hz), 35.3,
28.1, 24.2, 22.2. IR (KBr): νmax = 3261, 3060, 2975, 1731, 1613,
1462, 1535, 1300, 1258, 1157, 1090, 841, 748 cm–1. MS (EI): m/z
=
C
497.2 [M
22H29F3N2O4SNa: 497.1692; found: 497.1712.
+ +
Na]+. ESI-HRMS: m/z [M Na]+ calcd for
(17) Trost, B. M.; Cramer, N.; Silverman, S. M. J. Am. Chem. Soc. 2007,
129, 12396.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 67–72