Organic Letters
Letter
(
2) (a) Kamitani, M.; Itazaki, M.; Tamiya, C.; Nakazawa, H. J. Am.
Chem. Soc. 2012, 134, 11932. (b) Di Giuseppe, A.; De Luca, R.;
Castarlenas, R.; Perez-Torrente, J. J.; Crucianelli, M.; Oro, L. A. Chem.
coupling (ca. 1000 Hz) was observed by 31P and 19F NMR. See the
Supporting Information for details.
(16) See the Supporting Information for details.
(17) The obtained phosphine sulfides can be readily desulfidated to
the corresponding phosphines (a) Zablocka, M.; Delest, B.; Igau, A.;
Skowronska, A.; Majoral, J.-P. Tetrahedron Lett. 1997, 38, 5997.
(b) Saito, M.; Nishibayashi, Y.; Uemura, S. Organometallics 2004, 23,
4012. Aso see refs 4c and 7.
́
Commun. 2016, 52, 5554. (c) Yuan, J.; Zhu, L.; Zhang, J.; Li, J.; Cui, C.
Organometallics 2017, 36, 455. While somewhat limited in scope, KO-
t-Bu is also known to promote the double hydrophosphination, see:
(
d) Bookham, J. L.; McFarlane, W.; Thornton-Pett, M.; Jones, S. J.
Chem. Soc., Dalton Trans. 1990, 3621. (e) Bookham, J. L.; Smithies, D.
M.; Wright, A.; Thornton-Pett, M.; McFarlane, M. J. Chem. Soc.,
Dalton Trans. 1998, 811.
(
3) (a) Sato, A.; Yorimitsu, H.; Oshima, K. Angew. Chem., Int. Ed.
2
005, 44, 1694. (b) Kawaguchi, S.-i.; Nagata, S.; Shirai, T.; Tsuchii, K.;
Nomoto, A.; Ogawa, A. Tetrahedron Lett. 2006, 47, 3919. (c) Okugawa,
Y.; Hirano, K.; Miura, M. Org. Lett. 2017, 19, 2973. For noncatalyzed
diphosphination of specially activated alkynes including dimethyl
acetylenedicarboxylate and methyl propiolate, see: (d) Dodds, D. L.;
Haddow, M. F.; Orpen, A. G.; Pringle, P. G.; Woodward, G.
Organometallics 2006, 25, 5937.
(
4) (a) King, R. B.; Kapoor, P. N. J. Am. Chem. Soc. 1971, 93, 4158.
b) Carty, A. J.; Johnson, D. K.; Jacobson, S. E. J. Am. Chem. Soc. 1979,
01, 5612. (c) Kondoh, A.; Yorimitsu, H.; Oshima, K. J. Am. Chem.
Soc. 2007, 129, 4099.
5) For classical methods with highly reactive PCl , Cl P−PCl , F P−
(
1
(
3
2
2
2
PF , or Me P−PMe under harsh conditions, see: (a) Chatt, J.;
2
2
2
Hussain, W.; Leigh, G. J.; Ali, H. M.; Picket, C. J.; Rankin, D. A. J.
Chem. Soc., Dalton Trans. 1985, 1131. (b) Burg, A. B. J. Am. Chem. Soc.
1
961, 83, 2226. (c) Drieß, M.; Haiber, G.; Anorg, Z. Z. Anorg. Allg.
Chem. 1993, 619, 215. (d) Morse, K. W.; Morse, J. G. J. Am. Chem. Soc.
973, 95, 8469.
6) For application of silylphosphines in C−P bond formations, see:
a) Hayashi, M.; Matsuura, Y.; Watanabe, Y. J. Org. Chem. 2006, 71,
1
(
(
9
248. (b) Lamas, M.-C.; Studer, A. Org. Lett. 2011, 13, 2236.
(
c) Hirano, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2004, 6, 4873.
7) Okugawa, Y.; Hirano, K.; Miura, M. Angew. Chem., Int. Ed. 2016,
5, 13558.
8) Sato, Y.; Kawaguchi, S.-i.; Nomoto, A.; Ogawa, A. Angew. Chem.,
Int. Ed. 2016, 55, 9700.
9) For selected recent reviews and accounts, see: (a) Yoon, T. P.;
(
5
(
(
Ischay, M. A.; Du, J. Nat. Chem. 2010, 2, 527. (b) Narayanam, J. M. R.;
Stephenson, C. R. J. Chem. Soc. Rev. 2011, 40, 102. (c) Prier, C. K.;
Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322.
(
(
d) Ravelli, D.; Protti, S.; Fagnoni, M. Chem. Rev. 2016, 116, 9850.
e) Koike, T.; Akita, M. Acc. Chem. Res. 2016, 49, 1937. Recent
advances in organophosphorous chemistry under photoredox catalysis:
f) Luo, K.; Yang, W.-C.; Wu, L. Asian J. Org. Chem. 2017, 6, 350.
10) Crystallographic data for the structure have been deposited with
(
(
the Cambridge Crystallographic Data Centre (CCDC 1562909). See
the Supporting Information for details.
(
11) Unfortunately, attempts to apply aliphatic internal alkenes such
as cyclohexene remained unsuccessful. The reaction with Me Si-PCy
3
2
also formed no corresponding phosphinated product.
(
12) Only a trace amount of free F−PPh was also observed, but it
2
gradually disappeared. See the Supporting Information for details.
13) (a) Holthausen, M. H.; Mehta, M.; Stephan, D. W. Angew.
Chem., Int. Ed. 2014, 53, 6538. (b) Firth, K. F.; Mobus, J.; Stephan, D.
(
̈
W. Chem. Commun. 2016, 52, 13967. (c) Solyntjes, S.; Neumann, B.;
Stammler, H.-G.; Ignat’ev, N.; Hoge, B. Eur. J. Inorg. Chem. 2016,
2
(
016, 3999.
14) We also monitored the stoichiometric reaction of H-PPh or
2
19
31
Ph P-PPh with NFSI in DCE-d by F and P NMR. The reaction of
2
2
4
H-PPh and NFSI formed a large amount of free F-PPh and Ph P-
2
2
2
PPh , which are inactive species toward the desired vic-diphosphina-
2
tion. On the other hand, the mixture of Ph P-PPh and NFSI showed
2
2
1
9
31
F and P NMR spectra similar to those from Me Si-PPh and NFSI.
3
2
Thus, we cannot provide conclusive statements at present. See the
Supporting Information for details.
(
15) The formed diphosphinated species 3a can coordinate to the
regenerated NFSI: actually, upon treatment of bis(diphenylphospho-
1
no)ethane (DPPE) with NFSI in CDCl , the corresponding JPF
3
D
Org. Lett. XXXX, XXX, XXX−XXX