N. Iwadate, M. Suginome / Journal of Organometallic Chemistry 694 (2009) 1713–1717
1717
J = 1.6 Hz, 1H); 13C NMR (125 MHz, CDCl3) d 106.8, 118.8, 120.4,
(500.0 MHz, C6D6) d 0.85 (t, J = 7.0 Hz, 24H), 1.17–1.25 (m, 32H),
1.28–1.34 (m, 16H), 1.62 (quint, J = 6.5 Hz, 16H), 3.67 (t,
J = 6.3 Hz, 16H), 5.66 (br s, 2H), 6.02 (d, 5.5 Hz, 2H), 6.91 (dd,
J = 8.5, 1.5 Hz, 8H), 7.05–7.10 (m, 4H), 7.20 (t, J = 8.0 Hz, 8H), 7.26
(d, J = 8.0 Hz, 8H), 7.41 (s, 8H), 7.90 (s, 2H), 8.03 (s, 4H), 8.10 (d,
J = 1.5 Hz, 8H), 8.15 (s, 2H), 8.19 (d, J = 1.5 Hz, 4H), 8.30 (s, 1H);
13C NMR (125 MHz, CDCl3) d 14.5, 23.1, 26.2, 29.8, 32.1, 68.6,
106.7, 114.0, 114.2, 118.4, 120.2, 120.5, 126.0, 126.1, 126.5,
128.1, 129.2, 130.3, 130.5, 136.8, 141.4, 142.4, 142.6, 142.9,
143.0, 143.1, 143.2, 160.1; HRMS (FAB) m/z Calc. for C76H85BN2O4
(M+): 2109.2659, found: 2110.2773.
125.8, 127.3, 128.1, 131.8, 134.2, 136.8, 137.0, 141.0; 11B NMR
(128 MHz, CDCl3)
d 28.9; IR (KBr) 3421, 1599, 1409, 1237,
1087 cmꢁ1
;
HRMS (EI) m/z Calc. for C16H11BBr2N2 (M+):
399.9382, found: 399.9391. Compound 2h: 1H NMR (CDCl3) d
1.43 (t, J = 7.2 Hz, 3H), 4.43 (q, J = 7.2 Hz, 2H), 6.04 (br s, 2H),
6.42 (d, J = 6.8 Hz, 2H), 7.07 (d, J = 8.4 Hz, 2H), 7.14 (dd, J = 6.8,
8.4 Hz, 2H), 7.91 (s, 1H), 8.21 (s, 1H), 8.24 (d, J = 1.2 Hz, 1H); 13C
NMR (125 MHz, CDCl3) d 14.8, 62.1, 106.8, 118.8, 120.4, 123.4,
128.1, 131.5, 132.6, 134.4, 136.7, 138.9, 140.9, 165.8; 11B NMR
(128 MHz, CDCl3) d 29.0; IR (KBr) 3378, 1708, 1605, 1405, 1222,
1034 cmꢁ1
; HRMS (EI) m/z Calc. for C19H16BBrN2O2 (M+):
394.0488, found: 394.0488. Compound 2i: 1H NMR (400.0 Hz,
CDCl3) d 3.84 (s, 3H), 5.94 (br s, 2H), 6.40 (d, J = 7.2 Hz, 2H),
7.06–7.08 (m, 3H), 7.13–7.16 (m, 3H), 7.32 (s, 1H); 13C NMR
(125 MHz, CDCl3) d 56.01, 106.7, 116.6, 118.6, 118.8, 120.4,
123.8, 126.7, 128.1, 136.8, 141.1, 160.7; 11B NMR (128 MHz, CDCl3)
4.4. Typical procedure for the unmasking
To a solution of 4 (1.02 g, 1.7 mmol) in THF (41 mL) was added
HCl aq (5 N, 4.1 mL, 21 mmol) at room temperature. The homoge-
neous mixture was stirred at room temperature for 8 h, leading to
the formation of precipitation in the solution. To the mixture was
added HCl aq (3 N, 30 mL), and the suspension was filtered through
a pad of Celite. The filtrate was extracted with Et2O twice. The or-
ganic layer was dried over magnesium sulfate and evaporated un-
der vacuum. The material (843 mg, 95% yield) was essentially pure
by 1H NMR determination and used for the cross-coupling reaction
without further purification.
d
29.1; IR (KBr) 3412, 1602, 1406, 1049 cmꢁ1; HRMS (EI) m/z Calc.
for C17H14BBrN2O (M+): 352.0383, found: 352.0382. Compound 2j:
1H NMR (CDCl3) d 5.98 (br s, 2H), 6.42 (dd, J = 7.2, 1.0 Hz, 2H), 7.09
(dd, J = 7.8, 1.0 Hz, 3H), 7.17 (dd, J = 7.8, 7.2 Hz, 2H), 7.25–7.27 (m,
1H), 7.51 (dd, J = 3.2, 0.8 Hz, 1H), 7.63 (dd, 4.4, 0.8 Hz, 1H); 13C
NMR (125 MHz, CDCl3) d 106.6, 118.4, 120.2, 128.0, 129.0, 130.5,
133.3, 136.8, 141.2; 11B NMR (128 MHz, CDCl3) d 27.2; IR (KBr)
3402, 1598, 1415, 1233, 1067 cmꢁ1; HRMS (EI) m/z Calc. for
C14H11BN2S (M+): 250.0736, found: 250.0744.
References
[1] (a) N. Miyaura, Top. Curr. Chem. 219 (2002) 11;
4.3. Typical procedure for the cross-coupling. Synthesis of 4
(b) A. Suzuki, H.C. Brown, Organic Synthesis via Boranes, vol. 3, Aldrich,
Milwaukee, WI, 2003;
To a solution of Pd(OAc)2 (34 mg, 0.15 mmol), S-Phos (2-dicy-
(c) N. Miyaura, A. Suzuki, Chem. Rev. 95 (1995) 2457.
clohexylphosphino-20,60-dimethoxybiphenyl,
123 mg,
0.300
[2] D. Hall, Boronic Acids, Wiley, Weinheim, Germany, 2005.
[3] (a) S. Ishikawa, K. Manabe, Chem. Lett. 35 (2006) 164;
(b) S. Ishikawa, K. Manabe, Chem. Commun. (2006) 2589.
[4] (a) H. Noguchi, K. Hojo, M. Suginome, J. Am. Chem. Soc. 129 (2007) 758;
(b) H. Noguchi, T. Shioda, C.-M. Chou, M. Suginome, Org. Lett. 10 (2008) 377.
[5] (a) E.P. Gillis, M.D. Burke, J. Am. Chem. Soc. 129 (2007) 6716;
(b) S.J. Lee, K.C. Gray, J.S. Paek, M.D. Burke, J. Am. Chem. Soc. 130 (2008) 466.
[6] (a) F.F. Caserio Jr., J.J. Cavallo, R.I. Wagner, J. Org. Chem. 26 (1961) 2157;
(b) G. Kaupp, M.R. Naimi-Jamal, V. Stepanenko, Chem. Eur. J. 9 (2003) 4156.
[7] (a) H. Chen, S. Schlecht, T.C. Semple, J.F. Hartwig, Science 287 (2000) 1995;
(b) S. Shimada, A.S. Batsanov, J.A.K. Howard, T.B. Marder, Angew. Chem., Int.
Ed. 40 (2001) 2168;
mmol), and K3PO4 (0.96 g, 4.5 mmol) in THF (13 mL) were added
2f (603 mg, 1.50 mmol), arylboronic acid 3 (1.0 g, 4.50 mmol),
and then water (0.27 mL, 15 mmol), and the mixture was stirred
at 80 °C for 24 h. To the cooled mixture was added water, and
the organic material was extracted with CH2Cl2. The organic layer
was dried over sodium sulfate and the solvent was evaporated un-
der vacuum. The crude product was purified by silica gel column
chromatography (hexane/CH2Cl2 = 2:1), affording coupling product
4 (842 mg, 94%). Compound 4: 1H NMR (CDCl3) d 0.911–0.95 (m,
6H), 1.35–1.40 (m, 8H), 1.50–1.53 (m, 4H), 1.84 (quint, J = 7.2 Hz,
4H), 4.06 (t, J = 6.4 Hz, 4H), 6.13 (br s, 2 H), 6.46 (dd, J = 7.6,
0.8 Hz, 2H), 6.95 (ddd, J = 8.0, 2.4, 0.8 Hz, 2H), 7.08 (dd, J = 8.4,
0.8 Hz, 2H), 7.17 (dd, J = 7.6, 8.4 Hz, 2H), 7.22–7.27 (m, 4H), 7.41
(t, J = 8.0 Hz, 2H), 7.81 (t, J = 0.8 Hz, 2H), 7.88 (t, J = 1.8 Hz, 1H);
13C NMR (125 MHz, CDCl3) d 14.5, 23.1, 26.3, 29.8, 32.1, 68.7,
106.6, 113.8, 114.4, 118.4, 120.1, 120.4, 128.1, 128.6, 129.9,
130.3, 136.8, 141.5, 142.1, 143.0, 160.1; 11B NMR (128 MHz, CDCl3)
(c) J.-Y. Cho, M.K. Tse, D. Holmes, R.E. Maleczka Jr., M.R. Smith III, Science 295
(2002) 305.
[8] (a) T. Ishiyama, M. Murata, N. Miyaura, J. Org. Chem. 60 (1995) 7508;
(b) T. Ishiyama, K. Ishida, N. Miyaura, Tetrahedron 57 (2001) 9813.
[9] (a) C.N. Iverson, M.R. Smith, J. Am. Chem. Soc. 121 (1999) 7696;
(b) J.-Y. Cho, C.N. Iverson, M.R. Smith, J. Am. Chem. Soc. 122 (2000) 12868;
(c) T. Ishiyama, J. Takagi, K. Ishida, N. Miyaura, N.R. Anastasi, J.F. Hartwig, J.
Am. Chem. Soc. 124 (2002) 390.
[10] The original two-step procedure for the preparation of (dan)BH consisted of
reaction of trichloroborane with 1,8-diaminonaphthalene followed by
reduction with LiAlH4 (54% yield). F.F. Caserio Jr., J.J. Cavallo, R.I. Wagner, J.
Org. Chem. 26 (1961) 2157.
[11] Only one reaction has been reported in US patent for the use of (dan)BH in the
synthesis of organoboron compounds. It is used in the C–H borylation of
benzene in the presence of an (ind)Ir(cod) catalyst at 150 °C. M.R. Smith, III,
PCT WO 03/006158 A2.
[12] (a) T. Ishiyama, J. Takagi, J.F. Hartwig, N. Miyaura, Angew. Chem., Int. Ed. 41
(2002) 3056;
(b) T. Ishiyama, Y. Nobuta, J.F. Hartwig, N. Miyaura, Chem. Commun. (2003)
2924.
[13] (a) For isolation of tris(boryl)iridium(III) complexes and their intermediacy in
the catalytic C–H borylation, see: P. Nguyen, H.P. Blom, S.A. Westcott, N.J.
Taylor, T.B. Marder, J. Am. Chem. Soc. 115 (1993) 9329;
(b) T.M. Boller, J.M. Murphy, M. Hapke, T. Ishiyama, N. Miyauara, J.F. Hartwig,
J. Am. Chem. Soc. 127 (2005) 14263.
[14] S.M. Grayson, J.M.J. Fréchet, Chem. Rev. 101 (2001) 3819.
[15] T.M. Miller, T.X. Neenan, R. Zayas, H.E. Bair, J. Am. Chem. Soc. 114 (1992) 1018.
d
29.8; IR (KBr) 3402, 2929, 1602, 1415, 1203 cmꢁ1; HRMS (EI) m/z
Calc. for C40H45BN2O2 (M+): 596.3574, found: 596.3574. Com-
pound 5: 1H NMR (CDCl3) d 0.88–0.91 (m, 12H), 1.33–1.36 (m,
16H), 1.46–1.48 (m, 8H), 1.81 (quint, J = 7.4 Hz, 8H), 4.03 (t,
J = 6.4 Hz, 8H), 6.18 (br s, 2H), 6.49 (d, J = 7.2 Hz, 2H), 6.94 (m,
4H), 7.08 (d, J = 7.6 Hz, 2H), 7.16 (dd, J = 7.2, 7.6 Hz, 2H), 7.24–
7.26 (m, 4H), 7.30 (d, J = 8.0 Hz, 4H), 7.40 (t, J = 8.0 Hz, 4H), 7.83
(t, J = 1.6 Hz, 2H), 7.86 (d, J = 2.0 Hz, 4H), 7.94 (d, J = 2.0 Hz, 2H),
8.05 (t, J = 1.6 Hz, 1H); 13C NMR (125 MHz, CDCl3) d 14.5, 23.1,
26.2, 29.8, 32.1, 68.6, 106.7, 114.0, 114.3, 118.5, 120.2, 120.5,
126.0, 126.1, 128.1, 129.0, 130.3, 130.4, 136.8, 141.4, 142.4,
142.7, 142.9, 143.0, 160.1; HRMS (FAB) m/z Calc. for C76H85BN2O4
(M+): 1100.6602, found: 1100.6597. Compound 6: 1H NMR