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Table 3 Hydrophosphination of phenylisocyanates with secondary phos-
phines HPR2
isocyanates but also for isothiocyanates. We thought the key
condition of this reaction is neat (no solvent).
This work was supported by a Grant-in-Aid for Scientific
Research from JSPS (Category C, No. 16K05728 (M. I.)), and by
a Grant-in Aid for Scientific Research on Innovation Area
‘‘Stimuli-responsive Chemical Species for the Creation of Func-
tional Molecules’’ (No. 15H00957 (H. N.)) from JSPS, Japan.
Conflicts of interest
There are no conflicts to declare.
Notes and references
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primary phosphine with isocyanates. Single hydrophosphination
product 7 was obtained in 71% yield but this reaction required
significantly longer reaction times (eqn (2)). We thought that it
was due to a small amount of hexane existing in commercially
available H2PPh (see the ESI†). Compound 7 was a major product
even when H2PPh was treated with 2 equiv. of PhNCO.
3 For selected references, see: (a) M. Espinal-Viguri, A. K. King,
J. P. Lowe, M. F. Mahon and R. L. Webster, ACS Catal., 2016,
6, 7892; (b) A. DiGiuseppe, R. De Luca, R. Castarlenas, J. J. Perez-
Torrente, M. Crucianelli and L. A. Oro, Chem. Commun., 2016,
52, 5554; (c) C. A. Bange and R. Waterman, ACS Catal., 2016,
6, 6413; (d) A. M. Geer, A. L. Serrano, B. de Bruin, M. A. Ciriano
and C. Tejel, Angew. Chem., Int. Ed., 2015, 54, 472 (Angew. Chem.,
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4 For selected references, see: (a) M. B. Geeson, A. R. Jupp, J. E.
McGrady and J. M. Goicoechea, Chem. Commun., 2014, 50, 12281;
(2)
Finally, we demonstrated the hydrophosphination of
isothiocyanate in our system because the La catalyzed hydro-
phosphination has also been reported by Behrle and Schmidt.4
Reaction of phenylisothiocyanate with diphenylphosphine
HPPh2 in a 1 : 1 molar ratio afforded the corresponding
phosphinecarbothioamide 8 in 499% yield (eqn (3)).
ˇ
ˇ
ˇ
ˇ
ˇ
ˇ
(b) P. Stepnicka, Chem. Soc. Rev., 2012, 41, 4273; (c) P. Stepnicka,
Coord. Chem. Rev., 2017, 353, 223; (d) O. Ku¨hl, Coord. Chem. Rev.,
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5 S. V. F. Beddoe, S. D. Cosham, A. N. Kulak, A. R. Jupp, J. M.
Goicoechea and G. Hyett, Dalton Trans., 2018, 47, 9221.
6 S. A. Buckler, J. Org. Chem., 1959, 24, 1460.
7 A. C. Behrle and J. A. R. Schmidt, Organometallics, 2013, 32, 1141.
8 H. R. Sharpe, A. M. Geer, W. Lewis, A. J. Blake and D. L. Kays, Angew.
Chem., Int. Ed., 2017, 56, 4845.
(3)
9 I. S. Karmel, M. Tamm and M. S. Eisen, Angew. Chem., Int. Ed., 2015,
54, 12422.
10 R. J. Batrice and M. S. Eisen, Chem. Sci., 2016, 7, 939.
11 X. Gu, L. Zhang, X. Zhu, S. Wang, S. Zhou, Y. Wei, G. Zhang, X. Mu,
Z. Huang, D. Hong and F. Zhang, Organometallics, 2015, 34, 4553.
12 Y. Zhang, L. Qu, Y. Wang, D. Yuan, Y. Yao and Q. Shen, Inorg. Chem.,
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13 M. Kamitani, M. Itazaki, C. Tamiya and H. Nakazawa, J. Am. Chem.
Soc., 2012, 134, 11932.
14 M. Itazaki, S. Katsube, M. Kamitani and H. Nakazawa, Chem.
Commun., 2016, 52, 3163.
It has been reported that a secondary phosphine reacts with
aldehyde at room temperature using neat reagents to afford
a-hydroxyphosphine via nucleophilic attack of phosphine phos-
phorus to carbonyl carbon.17 In our cases, it can be similarly
considered that the phosphine phosphorus nucleophilically
attacks the carbon in isocyanates, and then the hydrogen
on the phosphorus migrates to the amine nitrogen to give
phosphinecarboxamide.
15 A. M. Sheldrick, SHELXL-2014-Programs for Crystal Structure Analysis,
¨
In summary, we found a convenient synthesis of phosphi-
necarboxamide by hydrophosphination of isocyanates. This
system shows shorter reaction time, high yield, and good
functional group tolerance, and is applicable not only for
Gottingen, Germany, 2014.
16 A. R. Jupp and J. M. Goicoechea, J. Am. Chem. Soc., 2013, 135, 19131.
17 For selected recent examples, see: (a) D. V. Moiseev, P. Marcazzan
and B. R. James, Can. J. Chem., 2009, 87, 582; (b) D. V. Moiseev,
B. O. Patrick and B. R. James, Inorg. Chem., 2007, 46, 11467.
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