T.A. Boebel, J.F. Hartwig / Tetrahedron 64 (2008) 6824–6830
6829
1.00 mmol) to give 10o (140 mg, 83%) as an off white solid. 1H NMR
(CD3OD)
8.08 (d, 2H, J¼8.4 Hz), 7.56 (d, 2H, J¼8.4 Hz), 6.60 (d, 2H,
J¼2.0 Hz), 6.51 (t, 1H, J¼2.0 Hz), 5.67 (s, 1H), 3.90 (s, 3H), 3.77 (s,
6H); 13C NMR (CD3OD)
167.7, 163.1, 143.3, 140.0, 131.9, 131.3, 128.5,
106.5, 101.4, 59.0, 56.0, 52.8; HRMS (ESI) m/z: Calcd for C17H20NO4
(MꢁCl)þ 302.1392, found 302.1395; HPLC analysis of acetylated 6o:
Diacel CHIRACEL AD-H, hexane/isopropanol 9:1, flow rate¼1.0 mL/
min, detection wavelength¼230 nm.
magnesium sulfate, filtered, and concentrated. Purified product
was obtained by silica gel chromatography, eluting with 14% ethyl
acetate in hexane, and then 25% ethyl acetate in hexane, to give 11
(144.3 mg, 75%) as a white solid. 1H NMR of the isolated material
indicated 87% de by integration of the benzylic protons. Rf¼0.57 in
d
d
25% ethyl acetate in hexane; 1H NMR (500, CDCl3)
d 7.58 (d, 2H,
J¼8.3 Hz), 7.51 (d, 2H, J¼8.3 Hz), 6.98 (s, 2H), 6.92 (s, 1H), 5.60 (d,
1H, J¼3.0 Hz), 3.70 (d, 1H, J¼2.9 Hz), 2.29 (s, 6H), 1.27 (s, 9H); 13C
NMR (CDCl3)
d
146.6, 140.3, 138.2, 129.7 (q, J¼32.1 Hz), 129.6, 127.5,
4.22. (R)-C-(3-Chloro-5-methyl-phenyl)-C-(4-
methoxycarbonyl-phenyl)-methyl-ammonium chloride (10p)
125.7 (q, J¼3.7 Hz), 125.5, 123.9 (q, J¼272.0 Hz), 61.8, 55.9, 22.5,
21.2; 19F NMR (CDCl3)
d
ꢁ63.8; HRMS (ESI) m/z: Calcd for
C
20H25F3NOS (MþH)þ 384.1609, found 384.1602.
The general procedure was followed with sulfinimine 8c
(133 mg, 0.498 mmol) and aryl boronic ester 6e (253 mg,
1.00 mmol) to give 10p (91 mg, 56%) as a red solid. 1H NMR (CD3OD)
Acknowledgements
d
8.09 (d, 2H, J¼8.1 Hz), 7.55 (d, 2H, J¼8.1 Hz), 7.27 (s, 2H), 7.21 (s,
We thank the NSF for funding, Advanced Asymmetrics for the
gift of (S)-tert-butanesulfinamide and both Frontier Scientific and
AllyChem for gifts of bis(pinacolato)diboron. We thank Dan Weix
for many helpful discussions.
1H), 5.74 (s, 1H), 3.90 (s, 3H), 2.35 (s, 3H); 13C NMR (CD3OD)
d
167.6,
142.9, 142.9, 139.9, 136.0, 132.0, 131.4, 130.8, 128.6, 127.7, 125.7, 58.4,
52.8, 21.2; HRMS (ESI) m/z: Calcd for C16H17ClNO2 (MꢁCl)þ
290.0948, found 290.0958; HPLC analysis of acetylated 10p: Diacel
CHIRACEL OD-H, hexane/isopropanol 9:1, flow rate¼0.5 mL/min,
detection wavelength¼230 nm.
References and notes
1. Friedel–Crafts Alkylation; Sheldon, R. A., van Bekkum, H., Eds.; Wiley-VCH: New
York, NY, 2001.
4.23. (R)-C-(3-Bromo-5-methoxy-phenyl)-C-(4-
2. Zaugg, H. E.; Horrom, B. W. J. Am. Chem. Soc. 1958, 80, 4317.
3. Ross, S. D.; Finkelstein, M.; Petersen, R. C. J. Org. Chem. 1966, 31, 133.
4. Sataty, I.; Peled, N.; Ben-Ishai, D. Isr. J. Chem. 1976, 13, 145.
5. Ali, I. A. I.; El Ashry, E. S. H.; Schmidt, R. R. Tetrahedron 2004, 60, 4773.
6. Johannsen, M. Chem. Commun. 1999, 2233.
7. Saaby, S.; Fang, X.; Gartherhood, N.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2000,
39, 4114.
8. Jiang, B.; Huang, Z.-G. Synthesis 2005, 2198.
9. Abid, M.; Teixeira, L.; To¨ro¨k, B. Org. Lett. 2008, 10, 933.
10. Murphy, J. M.; Tzschucke, C. C.; Hartwig, J. F. Org. Lett. 2007, 9, 757.
11. Tzschucke, C. C.; Murphy, J. M.; Hartwig, J. F. Org. Lett. 2007, 9, 761.
12. Murphy, J. M.; Liao, X.; Hartwig, J. F. J. Am. Chem. Soc. 2007, 129, 15434.
13. Gnas, Y.; Glorius, F. Synthesis 2006, 1899.
14. Enders, D.; Schubert, H.; Nuebling, C. Angew. Chem., Int. Ed. Engl. 1986, 98,
1118.
15. Laschat, S.; Kunz, H. J. Org. Chem. 1991, 56, 5883.
16. Higashiyama, K.; Inoue, H.; Takahashi, H. Tetrahedron Lett. 1992, 33,
235.
17. Boezio, A. A.; Solberghe, G.; Lauzon, C.; Charette, A. B. J. Org. Chem. 2003, 68,
3241.
18. Zhou, P.; Chen, B.-C.; Davis, F. A. Tetrahedron 2004, 60, 8003.
19. Liu, G.; Cogan, D. A.; Ellman, J. A. J. Am. Chem. Soc. 1997, 119, 9913.
20. Davis, F. A.; Zhang, Y.; Andemichael, Y.; Fang, T.; Fanelli, D. L.; Zhang, H. J. Org.
Chem. 1999, 64, 1403.
21. Ellman, J. A.; Owens, T. D.; Tang, T. P. Acc. Chem. Res. 2002, 35, 984.
22. Tang, T. P.; Ellman, J. A. J. Org. Chem. 1999, 64, 12.
23. Wang, Y.; He, Q.-F.; Wang, H.-W.; Zhou, X.; Huang, Z.-Y.; Qin, Y. J. Org. Chem.
2006, 71, 1588.
24. Truong, V. L.; Menard, M. S.; Dion, I. Org. Lett. 2007, 9, 683.
25. Chemla, F.; Ferreira, F. J. Org. Chem. 2004, 69, 8244.
26. Sun, X.-W.; Xu, M.-H.; Lin, G.-Q. Org. Lett. 2006, 8, 4979.
27. Weix, D. J.; Shi, Y.; Ellman, J. A. J. Am. Chem. Soc. 2005, 127, 1092.
28. Bolshan, Y.; Batey, R. A. Org. Lett. 2005, 7, 1481.
29. Boronic Acids: Preparation and Applications in Organic Synthesis and Medicine;
Hall, D. G., Ed.; Wiley-VCH: Weinheim, 2005.
methoxycarbonyl-phenyl)-methyl-ammonium chloride (10q)
The general procedure was followed with sulfinimine 8c
(133 mg, 0.498 mmol) and aryl boronic ester 6f (315 mg,
1.01 mmol) to give 10q (118 mg, 61%) as a beige solid. 1H NMR
(CD3OD)
7.16 (s, 1H), 7.02 (s, 1H), 5.74 (s, 1H), 3.90 (s, 3H), 3.80 (s, 3H); 13C
NMR (CD3OD) 167.6, 162.6, 142.8, 141.1, 132.1, 131.4, 128.6, 124.7,
d
8.09 (d, 2H, J¼8.3 Hz), 7.55 (d, 2H, J¼8.2 Hz), 7.18 (s, 1H),
d
123.5, 118.8, 113.7, 58.3, 56.4, 52.8; HRMS (ESI) m/z: Calcd for
C
16H17BrNO3 (MꢁCl)þ 350.0392, found 350.0392; HPLC analysis of
acetylated 10q: Diacel CHIRACEL AD-H, hexane/isopropanol 9:1,
flow rate¼1.0 mL/min, detection wavelength¼230 nm.
4.24. General procedure for the acetylation of a,a-diaryl
methylammonium chloride products (10a–10q) for chiral
HPLC analysis
A 1 dram vial was charged with
chloride (0.010 mmol), toluene (100
0.015 mmol), and triethylamine (4.2
a
m
m
,
a
-diaryl methylammonium
L), acetic anhydride (1.4 L,
L, 0.030 mmol) and allowed
L) was added, and the
crude mixture was filtered though a short plug of silica gel, rinsing
L). The combined filtrates were
m
to stir. After 40 min, diethyl ether (500
m
with more diethyl ether (3ꢂ500
m
concentrated by rotary evaporation and then under high vacuum to
give solid amide products that were used without further
purification.
30. Brown, H. C.; Cole, T. E. Organometallics 1983, 2, 1316.
31. Wong, K.-T.; Chien, Y.-Y.; Liao, Y.-L.; Lin, C.-C.; Chou, M.-Y.; Leung, M.-K. J. Org.
Chem. 2002, 67, 1041.
4.25. One-pot conversion of meta-xylene to sulfinyl amine 11
32. Sharp, M. J.; Cheng, W.; Snieckus, V. Tetrahedron Lett. 1987, 28, 5093.
33. Ishiyama, T.; Murata, M.; Miyaura, N. J. Org. Chem. 1995, 60, 7508.
34. Chen, H.; Schlecht, S.; Semple, T. C.; Hartwig, J. F. Science 2000, 287,
1995.
Inside a nitrogen-filled glove box, 20 mL vial was charged with
[Ir(cod)Cl]2 (1.7 mg, 0.0026 mmol), dtbpy (1.5 mg, 0.0056 mmol),
1,3,5-trimethoxybenzene (9.6 mg, 0.057 mmol), B2pin2 (215 mg,
35. Shimada, S.; Batsanov, A. S.; Howard, J. A. K.; Marder, T. B. Angew. Chem., Int. Ed.
2001, 40, 2168.
36. Iverson, C. N.; Smith, M. R., III. J. Am. Chem. Soc. 1999, 121, 7696.
37. Cho, J.-Y.; Tse, M. K.; Holmes, D.; Maleczka, R. E. J.; Smith, M. R., III. Science 2002,
295, 305.
38. Takagi, J.; Sato, K.; Hartwig, J. F.; Ishiyama, T.; Miyaura, N. Tetrahedron Lett.
2002, 43, 5649.
39. Ishiyama, T.; Takagi, J.; Yonekawa, Y.; Hartwig, J. F.; Miyaura, N. Adv. Synth. Catal.
2003, 345, 1103.
40. Ishiyama, T.; Nobuta, Y.; Hartwig, J. F.; Miyaura, N. Chem. Commun. 2003, 2924.
41. Mertins, K.; Zapf, A.; Beller, M. J. Mol. Catal. A: Chem. 2004, 207, 21.
42. Chotana, G. A.; Rak, M. A.; Smith, M. R., III. J. Am. Chem. Soc. 2005, 127,
10539.
0.847 mmol), THF (1.0 mL), and meta-xylene (122 mL, 0.997 mmol).
The resulting brown solution was heated at 80 ꢀC for 12 h, after
which time volatile materials were removed on high vacuum. To
the crude aryl boronic ester was added 8a (140 mg, 0.504 mmol),
[Rh(cod)(CH3CN)2]BF4 (9.6 mg, 0.025 mmol), dioxane (2.4 mL), and
triethylamine (140 mL, 1.00 mmol). The solution was then removed
from the glove box, whereupon water (2.4 mL) was added. After
22 h, TLC showed no further reaction, and the crude material was
diluted with water (50 mL), and extracted with ethyl acetate
(2ꢂ50 mL). The combined organic material was then dried over