Journal of the American Chemical Society
cooled to –30 °C and then mixed together. The resulting
Page 8 of 10
1
2
3
4
5
6
7
8
cloudy mixture was quickly filtered through Celite and all
volatiles were removed in vacuo to afford crude 5. (NMR
yield 70 %). The product was then dissolved in C6D6 and the
2521-2522. (c) Uematsu, N.; Fujii, A.; Hashiguchi, S.; Ikariya, T.;
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1
solution was monitored by 31P and H NMR1H NMR (C6D6,
500 MHz): δ 7.56 (d, 1H, J = 11.0 Hz), 7.40 (d, 1H, J = 11.0
Hz), 7.23-6.80 (m, 12H), 6.80 (d, 2H, J = 11.5 Hz), 6.67 (d,
1H, J = 10.5 Hz), 4.25 (broad s, 2H), 3.70 (broad s, 2H), 3.45
3
(s, 3H), 3.20 (s, 3H), 3.04 (d, 3H, JPH = 13.8 Hz), 1.16 (broad
s, 12H) ppm. 31P NMR (C6D6, 145 MHz): δ 105.2 ppm.
9
Synthesis of 8. Under nitrogen atmosphere, benzyl amine
(26 mg, 0.24 mmol) was added into a CH2Cl2 solution of 3 (50
mg, 120 mM). The resulting cloudy solution was quickly fil-
tered through Celite and all volatiles were removed in vacuo to
afford crude 8. The crude product was recrystallized in a 1:5
dichloromethane:pentane solution to afford 8 as a white crys-
tals (40 mg, 71 %). 1H NMR (CD2Cl2, 360 MHz): δ 7.40-7.21
(m, 3H), 7.08 (d, 1H, J = 7.0 Hz), 6.83 (t, 1H, J = 7.3 Hz),
6.68 (t, 1H, J = 7.6 Hz), 6.61 (d, 1H, J = 7.5 Hz), 6.56 (d, 1H,
J = 7.5 Hz), 3.07 (d, 3H, J = 10.3 Hz), 2.75 (s, 3H) ppm, 1.17
(s, 12H). 31P NMR (CD2Cl2, 145 MHz): δ 91.34 ppm. 13C
NMR (CD2Cl2, 125 MHz): δ 144.5, 143.9, 140.9, 129.3, 129.0,
10
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18
19
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23
24
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27
28
29
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31
32
33
34
35
36
37
38
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41
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43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2
128.3 (d, JPC = 11.3 Hz), 127.4, 127.0, 126.8, 126.5, 126.2,
125.2, 118.7, 117.3, 106.0, 82.6, 46.4, 44.8, 35.9, 29.0 (d, 2JPC
= 21.2 Hz), 24.3 ppm. MS (ESI) C27H35BN4O2P (M++H)
calc’d: 489.2591; found 489.2595.
13 Nifantiev, E. E.; Grachev, M. K.; Burmistrov, S. Y. Chem. Rev.
2000, 100, 3755–3800.
14 Power, P. P. Nature 2010, 463, 171–177.
15 Myers, T. W.; Berben, L. A. J. Am. Chem. Soc. 2013, 135,
9988–9990.
ASSOCIATED CONTENT
1
Supporting Information. Full experimental procedures; H, 13C,
16 W. Myers, T.; A. Berben, L. Chem. Sci. 2014, 5 (7), 2771–2777.
17 Zhao, W.; McCarthy, S. M.; Lai, T. Y.; Yennawar, H. P.; Ra-
dosevich, A. T. J. Am. Chem. Soc. 2014, 136 (50), 17634-17644.
18 Burck, S.; Gudat, D.; Nieger, M.; Du Mont, W.-W. J. Am. Chem.
Soc. 2006, 128, 3946–3955.
19 (a) Chong, C. C.; Hirao, H.; Kinjo, R. Angew. Chem. Int. Ed.
2014, 53, 3342–3346. (b) Chong, C. C.; Hirao, H.; Kinjo, R. Angew.
Chem. Int. Ed. 2015, 54, 190–194.
and 31P NMR spectra for all synthetic compounds; NOESY spec-
tra for 2; crystallographic details. This material is available free of
AUTHOR INFORMATION
Corresponding Author
* radosevich@mit.edu
20 Adams, M. R.; Tien, C.-H.; Huchenski, B. S. N.; Ferguson, M. J.;
Speed, A. W. H. Angew. Chem. Int. Ed. 2017, doi:
10.1002/anie.201611570.
ACKNOWLEDGMENT
21 Gudat, D. Acc. Chem. Res. 2010, 43, 1307–1316.
22 Snow, S. S.; Jiang, D. X.; Parry, R. W. Inorg. Chem. 1985, 24,
1460–1463.
23 A unidentified trace impurity from the in situ preparation of 2,
whose concentration does not change with time, is also observed in
31P NMR at δ 140.1 ppm.
The stoichiometric reactivity of 1 with HBpin was supported un-
der NSF award CHE-1724505. The catalytic hydroboration stud-
ies were supported under NIH grant GM114547. A.T.R. gratefully
acknowledges additional support from the Alfred P. Sloan Foun-
dation and Amgen. We thank Dr. Nicole L. Dunn (PSU) for pre-
liminary experiments.
24 (a) Keaton, R. J.; Blacquiere, J. M.; Baker, R. T. J. Am. Chem.
Soc. 2007, 129, 1844–1845. (b) Pun, D.; Lobkovsky, E.; J. Chirik, P.
Chem. Commun. 2007, 0, 3297–3299. (c) Chaplin, A. B.; Weller, A.
S. Angew. Chem. Int. Ed. 2010, 49, 581–584.
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