(s, C(CH3)3), 154.8 (s, Cipso NPh), 163.7 ppm (dd, 2J(P,C) = 18 Hz,
2J(P,C) = 4 Hz, CQNPh); 31P{1H} NMR (121.4 MHz, CD2Cl2,
25 1C): d = 27.4 (d, 2J(P,P) = 52 Hz, Ph2PQO), 57.1 ppm (d, 2J(P,P) =
52 Hz, Ph2PQC). 3b: 1H NMR (300 MHz, CDCl3, 25 1C): d = 0.97
(s, 9H, CH3 (tBu)), 1.90 (s, 6H, CH3 (Xylyl)), 3.58 (d, 3J(P,H) = 8 Hz,
2H, CH2), 6.7–8.1 ppm (23H, aryl); 13C{1H} NMR (75.5 MHz,
CDCl3, 25 1C): d = 18.8 (s, CH3 (Xylyl)), 29.5 (s, CH3 (tBu)),
52.7 (t, 2J(P,C) = 3J(P,C) = 10 Hz, CH2), 56.0 (s, C(CH3)3), 152.5
(s, Cipso NXylyl), 162.2 ppm (br, CQNXylyl); 31P{1H} NMR
(121.4 MHz, CD2Cl2, 25 1C): d = 29.3 (d, 2J(P,P) = 52 Hz, Ph2PQO),
58.5 ppm (d, 2J(P,P) = 52 Hz, Ph2PQC). 3c: 1H NMR (300 MHz,
CD2Cl2, 25 1C): d = 3.81 (d, 3J(P,H) = 8 Hz, 2H, CH2), 4.09
(d, 3J(P,H) = 7 Hz, 2H, CH2), 6.63 (d, 3J(H,H) = 7 Hz, 2H, Hortho
NPh), 6.78 (t, 3J(H,H) = 7 Hz, 1H, Hpara NPh), 6.7–8.0 ppm
(27H, Ph); 31P{1H} NMR (121.4 MHz, CD2Cl2, 25 1C): d = 27.4
(d, 2J(P,P) = 49 Hz, Ph2PQO), 62.2 ppm (d, 2J(P,P) = 49 Hz,
Ph2PQC). 3d: 1H NMR (300 MHz, CDCl3, 25 1C): d = 1.71
(s, 6H, CH3 (Xylyl)), 2.10 (s, 6H, CH3 (Xylyl)), 3.86 (d, 3J(P,H) = 7 Hz,
2H, CH2), 6.7–8.1 ppm (26H, aromatics); 13C{1H} NMR (75.5 MHz,
CDCl3, 25 1C): d = 18.4 (s, CH3 (Xylyl)), 18.8 (s, CH3 (Xylyl)), 50.7
(t, 1J(P,C) = 110 Hz, P2C), 58.9 (t, 2J(P,C) = 3J(P,C) = 11 Hz, CH2),
T = 293(2) K, ymax = 70, independent reflections = 6543, refined
parameters = 546, largest diff. peak and hole 0.31 and ꢀ0.41 e Aꢀ3
wR2 = 0.129, R1 = 0.048.
,
1 J. Ruiz, V. Riera, M. Vivanco, M. Lanfranchi and A. Tiripicchio,
Organometallics, 1998, 17, 3835.
2 J. Ruiz, F. Marquı
and M. R. Dıaz, Angew. Chem., Int. Ed., 2000, 39, 1821; J. Ruiz,
F. Marquınez, V. Riera, M. Vivanco, S. Garcıa-Granda and
M. R. Dıaz, Chem.–Eur. J., 2002, 8, 3872.
3 M. E. G. Mosquera, J. Ruiz, G. Garcı
Chem.–Eur. J., 2006, 12, 7706.
nez, V. Riera, M. Vivanco, S. Garcıa-Granda
´ ´
´
´
´
´
´
a and F. Marquınez,
´
4 J. Ruiz, V. Riera, M. Vivanco, M. Lanfranchi and A. Tiripicchio,
Angew. Chem., Int. Ed., 2005, 44, 102.
5 A. Domling and I. Ugi, Angew. Chem., Int. Ed., 2000, 39, 3169;
¨
¨
A. Domling, Chem. Rev., 2006, 106, 17; A. V. Gulevich,
A. G. Zhdanko, R. V. A. Orru and V. G. Nenajdenko, Chem.
Rev., 2010, 110, 5235.
6 A. M. Santos, C. C. Romao and F. E. Kuhn, J. Am. Chem. Soc.,
2003, 125, 2414.
¨
7 For the synthesis of 1,2-azaphospholene derivatives see for instance:
R. Streubel, H. Wilkens, F. Ruthe and P. G. Jones, Organometallics,
2006, 25, 4830, and references therein.
8 T. Kawashima, K. Kato and R. Okazaki, J. Am. Chem. Soc., 1992,
114, 4008.
9 Unfortunately we have been unable to obtain crystals of 4a
suitable for X-ray analysis, which would confirm definitively the
proposed structure for this compound, perhaps owing to its
extreme solubility in most organic solvents and to the pronounced
tendency to evolve to compound 3a with traces of water. For a
related structurally characterized 1,2,l5-azaphosphetidine see:
T. Kawayki, T. Soda and R. Okazaki, Angew. Chem., Int. Ed.
Engl., 1996, 35, 1096; N. Kano, A. Kikuchi and T. Kawashima,
Chem. Commun., 2001, 2096.
10 For a review see: D. Moderhack, Synthesis, 1985, 12, 1083.
11 J. Zhu, Eur. J. Org. Chem., 2003, 1133.
12 For reversible cycloaddition processes involving diphosphino-
ketenimines see ref. 2.
13 Oxidative additions of alcohols to phosphines have been described:
B. Tangour, C. Malavaud, M. T. Boisdon and J. Barrans,
Phosphorus, Sulfur Silicon Relat. Elem., 1989, 45, 189; A. F. Janzen
and L. Kruczynski, Can. J. Chem., 1979, 57(14), 1903; M. T. Boisdon,
C. Malavaud, F. Mathis and J. Barrans, Tetrahedron Lett., 1977, 39,
3501.
14 For a theoretical study on the addition of water to phosphines
forming P(V) derivatives see: E. W. Evans, W. O. George and
J. A. Platts, THEOCHEM, 2005, 730, 185.
2
151.7 (s, Cipso NXylyl), 163.0 ppm (d, J(P,C) = 13 Hz, CQNXylyl);
31P{1H} NMR (121.4 MHz, CD2Cl2, 25 1C): d = 26.1 (d, 2J(P,P) = 46 Hz,
Ph2PQO), 60.4 ppm (d, 2J(P,P) = 46 Hz, Ph2PQC). 4a: 1H NMR
(300 MHz, CD2Cl2, 25 1C): d = 0.62 (s, 9H, CH3 (tBu)), 1.56
(t, 3J(H,H) = 7 Hz, 3H, OCH2CH3), 4.65 (q, 3J(P,H) = 3J(H,H) =
7 Hz, 2H, OCH2CH3), 6.2–7.9 ppm (26H, Ph and CQCH); 13C{1H}
NMR (75.5 MHz, CD2Cl2, 25 1C): d = 17.3 (d, 3J(P,C) = 7 Hz,
OCH2CH3), 28.9 (s, CH3 (tBu)), 52.8 (d, 1J(P,C) = 18 Hz, P2C),
58.2 (s, C(CH3)3), 65.7 (d, 2J(P,C) = 6 Hz, OCH2CH3), 152.2
(s, Cipso NPh), 156.6 (d, 2J(P,C) = 12 Hz, CQCH), 169.2 ppm
(dd, 2J(P,C) = 8 Hz, 2J(P,C) = 2 Hz, C–NPh); 31P{1H} NMR
(121.4 MHz, CD2Cl2, 25 1C): d = ꢀ14.5 (d, 2J(P,P) = 181 Hz,
Ph2PQO), 57.8 ppm (d, 2J(P,P) = 181 Hz, Ph2PQC). 5a: 1H NMR
(300 MHz, CD2Cl2, 25 1C): d = 0.86 (s, 9H, CH3 (tBu)), 1.56
(t, 3J(H,H) = 7 Hz, 3H, OCH2CH3), 2.87 (s, 2H, CH2), 4.76
(q, 3J(P,H) = 3J(H,H) = 7 Hz, 2H, OCH2CH3), 6.0–7.9 ppm
(25H, Ph); 13C{1H} NMR (75.5 MHz, CD2Cl2, 25 1C): d = 16.6
(d, 3J(P,C) = 6 Hz, OCH2CH3), 28.7 (s, CH3 (tBu)), 44.2 (d, 2J(P,C) =
8 Hz, CH2), 50.6 (s, C(CH3)3), 65.5 (d, 2J(P,C) = 6 Hz, OCH2CH3),
151.2 (s, Cipso NPh), 172.1 ppm (d, 2J(P,C) = 8 Hz, CQNPh); 31P{1H}
NMR (121.4 MHz, CDCl3, 25 1C): d = 21.4 (d, 2J(P,P) = 54 Hz,
2
Ph2PQO), 50.6 ppm (d, J(P,P) = 54 Hz, Ph2PQC).
y Crystal data for 3a (C37H36N2OP2ꢁCH2Cl2): M = 671.54, crystal
size 0.13 ꢂ 0.10 ꢂ 0.08 mm, a = 11.6478(6) A, b = 18.985(1) A, c =
16.179(1) A, b = 99.847(4)<, V = 3525.0(4) A3, rcalcd = 1.265 g cmꢀ3
,
m = 2.76 mmꢀ1, Z = 4, monoclinic, space group P21/n, l = 1.54184 A,
c
4272 Chem. Commun., 2011, 47, 4270–4272
This journal is The Royal Society of Chemistry 2011