2856
L. Ackermann, H. K. Potukuchi
LETTER
Weissman, S. A.; Stauffer, S. R.; Burgey, C. S. Org. Lett.
2009, 11, 345. (c) For recent examples of cross-coupling
reactions with MIDA boronates, see: Knapp, D. M.; Gillis,
E. P.; Burke, M. D. J. Am. Chem. Soc. 2009, 131, 6961.
(18) (a) Ackermann, L.; Althammer, A. Chem. Unserer Zeit
2009, 43, 74. (b) Ackermann, L.; Born, R.; Spatz, J. H.;
Althammer, A.; Gschrei, C. J. Pure Appl. Chem. 2006, 78,
209.
Acknowledgment
Support by the DFG, the DAAD (fellowship to H.K.P.), and the
German-Israeli-Foundation (GIF) is gratefully acknowledged.
References and Notes
(1) Modern Arylation Methods; Ackermann, L., Ed.; Wiley-
VCH: Weinheim, 2009.
(19) Ackermann, L. Synlett 2007, 507.
(20) For selected recent representative examples, see:
(a) Ackermann, L.; Mulzer, M. Org. Lett. 2008, 10, 5043.
(b) Ackermann, L.; Althammer, A.; Born, R. Angew. Chem.
Int. Ed. 2006, 45, 2619. (c) Ackermann, L.; Gschrei, C. J.;
Althammer, A.; Riederer, M. Chem. Commun. 2006, 1419.
(d) Ackermann, L.; Althammer, A. Org. Lett. 2006, 8, 3457.
(e) Ackermann, L.; Born, R.; Spatz, J. H.; Meyer, D. Angew.
Chem. Int. Ed. 2005, 44, 7216. (f) Ackermann, L.; Born, R.
Angew. Chem. Int. Ed. 2005, 44, 2444.
(21) Surry, D. S.; Buchwald, S. L. Angew. Chem. Int. Ed. 2008,
47, 6338.
(22) Enders, D.; Tedeschi, L.; Bats, J. W. Angew. Chem. Int. Ed.
2000, 39, 4605.
(2) Transition Metals for Organic Synthesis, 2nd ed.; Beller, M.;
Bolm, C., Eds.; Wiley-VCH: Weinheim, 2004.
(3) Tsuji, J. Palladium Reagents and Catalysts, 2nd ed.; Wiley:
Chichester, 2004.
(4) Suzuki, A. J. Organomet. Chem. 1999, 576, 147.
(5) Littke, A. F. In Modern Arylation Methods; Ackermann, L.,
Ed.; Wiley-VCH: Weinheim, 2009, 25.
(6) Herrmann, W. A. Angew. Chem. Int. Ed. 2002, 41, 1290.
(7) N-Heterocyclic Carbenes in Synthesis; Nolan, S. P., Ed.;
Wiley-VCH: Weinheim, 2006.
(8) For selected recent examples of and reviews on palladium-
catalyzed Suzuki–Miyaura reactions with aryl-substituted
nucleophiles, see: (a) Organ, M. G.; Çalimsiz, S.; Sayah, M.;
Hoi, K. H.; Lough, A. J. Angew. Chem. Int. Ed. 2009, 48,
2383. (b) Diebolt, O.; Braunstein, P.; Nolan, S. P.; Cazin, C.
S. J. Chem. Commun. 2008, 3190. (c) So, C. M.; Lau, C. P.;
Kwong, F. Y. Angew. Chem. Int. Ed. 2008, 47, 8059.
(d) Martin, R.; Buchwald, S. L. Acc. Chem. Res. 2008, 41,
1461. (e) Doucet, H. Eur. J. Org. Chem. 2008, 2013; and
references cited therein.
(9) For representative recent examples involving the use of
heteroaromatic nucleophiles, see: (a) Molander, G. A.;
Canturk, B.; Kennedy, L. E. J. Org. Chem. 2009, 74, 973.
(b) Fleckenstein, C. A.; Plenio, H. J. Org. Chem. 2008, 73,
3236. (c) Billingsley, K.; Buchwald, S. L. J. Am. Chem. Soc.
2007, 129, 3358. (d) Billingsley, K. L.; Anderson, K. W.;
Buchwald, S. L. Angew. Chem. Int. Ed. 2006, 45, 3484.
(e) Kudo, N.; Perseghini, M.; Fu, G. C. Angew. Chem. Int.
Ed. 2006, 45, 1282; and references cited therein. (f) For
ligand-free Suzuki–Miyaura coupling reactions catalyzed by
Pd/C, see: Kitamura, Y.; Sako, S.; Udzu, T.; Tsutsui, A.;
Maegawa, T.; Monguchi, Y.; Sajiki, H. Chem. Commun.
2007, 5069. (g) Maegawa, T.; Kitamura, Y.; Sako, S.; Udzu,
T.; Sakurai, A.; Tanaka, A.; Kobayashi, Y.; Endo, K.; Bora,
U.; Kurita, T.; Kozaki, A.; Monguchi, Y.; Sajiki, H. Chem.
Eur. J. 2007, 13, 5937.
(23) Linghu, X.; Potnick, J. R.; Johnson, J. S. J. Am. Chem. Soc.
2004, 126, 3070.
(24) Analytical Data for HASPO 6d: Mp 202.9–203.4 °C. 1H
NMR (300 MHz, CDCl3): d = 7.67–7.45 (m, 6 H), 7.19–7.15
(m, 2 H), 6.94–6.78 (m, 8 H), 6.89 (d, JH–P = 744 Hz, 1 H),
5.67 (d, J = 8.3 Hz, 1 H), 5.18 (d, J = 8.3 Hz, 1 H), 0.71
(s, 3 H), 0.68 (s, 3 H). 13C NMR (75 MHz, CDCl3): d = 162.5
(Cq, 1JF–C = 248 Hz), 162.5 (Cq, 1JF–C = 248 Hz), 162.3
(Cq, 1JF–C = 248 Hz), 162.3 (Cq, 1JF–C = 248 Hz), 139.3 (Cq,
4JF–C = 3 Hz), 139.3 (Cq, 4JF–C = 3 Hz), 138.7 (Cq, 4JF–C
=
3 Hz), 134.5 (Cq, 4JF–C = 3 Hz), 130.7 (CH, 3JF–C = 8 Hz),
130.0 (CH, 3JF–C = 8 Hz), 128.6 (CH, 3JF–C = 8 Hz), 128.6
(CH, 3JF–C = 8 Hz), 115.6 (CH, 2JF–C = 21 Hz), 115.4 (CH,
2JF–C = 22 Hz), 114.6 (Cq), 114.5 (CH, 2JF–C = 22 Hz), 114.3
(CH, 2JF–C = 22 Hz), 88.7 (Cq), 87.6 (Cq), 80.0 (CH), 79.5
(CH), 26.8 (CH3), 26.6 (CH3). 31P NMR (121 MHz, CDCl3):
d = –2.5. 19F NMR (282 MHz, CDCl3): d = –112.4 (m),
–112.9 (m), –113.9 (m), –114.1 (m). IR (KBr): 3424, 2993,
2903, 2354, 2344, 1601, 1506, 1268, 1161, 1082, 937, 847,
762 cm–1. HR-MS (ESI): m/z calcd for C31H24F4O5P:
583.1303; found: 583.1306.
(25) Synthesis of 3b (Table 2, entry 1); Typical procedure: A
suspension of Pd2dba3 (4.6 mg, 0.005 mmol, 1.0 mol%), 6d
(11.7 mg, 0.020 mmol, 4.0 mol%), K3PO4 (318 mg, 1.50
mmol), 1a (205 mg, 0.75 mmol), 2b (147 mg, 0.50 mmol) in
1,4-dioxane (2.0 mL) was stirred under N2 for 20 h at
110 °C. After the reaction mixture was cooled to ambient
temperature, MTBE (50 mL) and H2O (50 mL) were added.
The separated aqueous phase was extracted with MTBE
(3 × 50 mL). The combined organic layers were washed with
brine (50 mL), dried over Na2SO4 and concentrated in vacuo.
The remaining residue was purified by column chromatog-
raphy on silica gel (n-hexane–EtOAc, 9:1) to yield 3b (114
mg, 78%) as a white solid (mp 45.0 °C). 1H NMR (300 MHz,
CDCl3): d = 8.75 (dt, J = 4.8, 1.4 Hz, 1 H), 8.48 (s, 2 H), 7.91
(s, 1 H), 7.88–7.77 (m, 2 H), 7.40–7.29 (m, 1 H). 13C NMR
(75 MHz, CDCl3): d = 154.1 (Cq), 150.1 (CH), 141.3 (Cq),
(10) (a) Hapke, M.; Brandt, L.; Lützen, A. Chem. Soc. Rev. 2008,
37, 2782. (b) Tyrrell, E.; Brookes, P. Synthesis 2004, 469.
(11) Campeau, L.-C.; Fagnou, K. Chem. Soc. Rev. 2007, 36,
1058.
(12) Dubrovina, N. V.; Börner, A. Angew. Chem. Int. Ed. 2004,
43, 5883.
(13) Ackermann, L. Synthesis 2006, 1557.
(14) Ackermann, L. In Trivalent Phosphorus Compounds in
Asymmetric Catalysis, Synthesis and Applications; Börner,
A., Ed.; Wiley-VCH: Weinheim, 2008, 831.
(15) For representative recent examples of secondary phosphine
oxides as preligands in catalytic C–C bond formation, see:
(a) Xu, H.; Ekoue-Kovi, K.; Wolf, C. J. Org. Chem. 2008,
73, 7638. (b) Ackermann, L.; Vicente, R.; Althammer, A.
Org. Lett. 2008, 10, 2299. (c) Wolf, C.; Ekoue-Kovi, K.
Eur. J. Org. Chem. 2006, 1917. (d) Ackermann, L. Org.
Lett. 2005, 7, 3123. (e) Li, G. Y. Angew. Chem. Int. Ed.
2001, 40, 1513; and references cited therein.
137.2 (CH), 132.1 (Cq, 2JF–C = 33 Hz), 126.9 (CH, 3JF–C
=
4 Hz), 123.6 (CH), 123.4 (Cq, 1JF–C = 273 Hz), 122.3 (CH,
3JF–C = 4 Hz), 120.6 (CH). 19F NMR (282 MHz, CDCl3): d =
–62.9. IR (KBr): 3897, 2927, 1591, 1455, 1382, 1279, 1136,
897, 785, 683 cm–1. MS (EI): m/z (%) = 291 (100) [M+], 272
(22), 252 (10), 222 (38), 202 (12), 83 (28), 71 (34), 57 (66),
43 (64). HR-MS (EI): m/z calcd for C13H7F6N: 292.0555;
found: 292.0557. The spectral data were in accordance with
those reported in the literature.16
(16) Billingsley, K. L.; Buchwald, S. L. Angew. Chem. Int. Ed.
2008, 47, 4695.
(17) (a) Yang, D. X.; Colletti, S. L.; Wu, K.; Song, M.; Li, G. Y.;
Shen, H. C. Org. Lett. 2009, 11, 381. (b) See also: Deng, J.
Z.; Paone, D. V.; Ginnetti, A. T.; Kurihara, H.; Dreher, S. D.;
Synlett 2009, No. 17, 2852–2856 © Thieme Stuttgart · New York