S. W. Markowicz et al. / Tetrahedron: Asymmetry 17 (2006) 434–448
447
4.15. 1,3-Bis-[3a-(2a-methoxypinane)]benzimidazolium
chloride 9b
4.17. 1,3-Di-3a-(2a-methoxypinan)-2-phenyl-
[1,3,2]diazaphospholidine 2-oxide 10
0
A mixture of 0.481 g (0.002 mol) of N,N -bis-[3a-(2a-
methoxypinane)]benzene-1,2-diamine 8e dihydrochlo-
ride, 5 ml of triethyl orthoformate, and one drop of
A 150-ml flask equipped with a thermometer, septum, a
magnetic stirring bar, and continuously purged with
argon was charged with 0.94 g (0.0024 mol) dimethoxy-
diamine 8b and 0.70 ml (0.005 mol, 10% excess) of
triethylamine in 70 ml THF. The mixture was cooled
to 0 ꢁC and 0.35 ml (0.0026 mol, 7% excess) of dichloro-
phenylphosphine was added in portions via syringe.
The reaction continued at 0 ꢁC for 8 h and at room tem-
perature for the following 12 h. After this time, the mix-
ture was oxidized by bubbling dry air through the
solution over 3 h and the solvent removed in vacuo.
Then 100 ml of hexane was added and the undissolved
phenylphosphoric acid and triethylamine hydrochlo-
rides were filtered out. Evaporation of hexane afforded
9
6% formic acid was heated at 105 ꢁC for 64 h. The reac-
tion mixture was washed with ether and acetonitrile
2 · 5 ml). The vacuum-dried residue (0.210 g) was iden-
tified as the desired salt. Attempts to crystallize the
product failed; the product was characterized as an
(
0
9:9
1
enamel. H NMR d: 133 (s, 6H, CH ); 1.34 (s, 6H,
3
0
0
0
3;3
8
;8
10;10
CH ); 1.41 (s, 6H,
CH ); 5.66 (m, 2H,
CH);
3
3
arom.
im.
13
7
1
.49–7.58 (4H
); 11.11 (s, 1H, CH); C NMR d:
im.
47.77 ( C).
1
4
4
.16. X-ray crystallographic studies
1
0
.30 g of an oily residue. Flash chromatography yielded
20
.765 g (63%) of oily product. ½aꢁ ¼ þ11:3 (c 1,
D
4
.16.1. Crystal data for 6b. C H N O , M = 360.53,
monoclinic, space group P2 (No. 4), a = 12.646(3) A,
1
2
2
36
2
2
CHCl ); MS: M+1 = 505; H NMR d: 0.93 (s, 6H,
˚
3
0
0
0
1
9;9
8;8
10;10
CH
3
), 1.29 (s, 6H,
CH
3
), 1.53 (s, 6H,
CH
CH), 1.99–2.02 (m, 4H),
),
CH); 3.73–3.76 (m, 4H,
3
),
˚
˚
b = 12.554(3) A, c = 20.591(4) A, b = 98.8(3)ꢁ, V =
0
7
;7 b
3
3
1.75 (d, 2H, J7a,7b = 10.5,
2.13 (m, 2H), 2.36–2.39 (m, 4H), 3.18 (s, 6H, OCH
3
3
2
2
˚
230.4(13) A , Z = 6, D = 1.112 g/cm , T = 297 K,
x
3
ꢂ1
˚
l = 0.071 mm , k = 0.71073 A, F(000) = 1188, color-
less prisms (0.3 · 0.3 · 0.4 mm), data/parameters =
0,709/705; final R = 0.0657, wR = 0.2018 (all data).
0
;3 b
3
.49–3.52 (m, 2H,
aliph.
arom.
CH ), 7.31–7.60 (m, 3H,
CH), 7.88–7.92 (m,
2
1
arom.
31
1
2
H,
CH); P NMR d: 31.64.
4
.16.2. Crystal data for 6e. C H N O , M = 408.57,
26 36 2 2
˚
monoclinic, space group C2 (No. 5), a = 22.603(5) A,
b = 8.080(2) A, c = 14.011(3) A, c = 112.9(3)ꢁ, V =
2
l = 0.072 mm , k = 0.71073 A, F(000) = 888, color-
less prisms (0.2 · 0.2 · 0.3 mm), data/parameters =
3
References
˚
˚
3
3
˚
356.7(11) A , Z = 4, D = 1.511 g/cm , T = 297 K,
x
1. (a) Denmark, S. E.; Fu, J. Chem. Rev. 2003, 103, 2763–
2793; (b) Groger, H. Chem. Rev. 2003, 103, 2795–2827; (c)
Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829–
2844; (d) Rajan Babu, T. V. Chem. Rev. 2003, 103, 2845–
ꢂ1
˚
773/275; final R = 0.0424, wR = 0.0941 (all data).
1 2
2
2
860; (e) Davies, H. M. L.; Beckwith, R. E. J. Chem. Rev.
003, 103, 2861–2903; (f) Muller, P.; Fruit, C. Chem. Rev.
4
.16.3. Crystal data for 7a. C H N O , M = 388.58,
24 40 2 2
2003, 103, 2905–2919; (g) Trost, B. M.; Crawley, M. L.
Chem. Rev. 2003, 103, 2921–2943; (h) Dounay, A. B.;
Overman, L. E. Chem. Rev. 2003, 103, 2945–2963; (i)
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Lectka, T. Chem. Rev. 2003, 103, 2985–3012; (k) Mar-
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Tang, W.; Zhang, X. Chem. Rev. 2003, 103, 3029–3069;
orthorhombic, space group P2 2 2
a = 7.646(2) A, b = 10.927(2) A, c = 27.051(5) A, V =
2
0
prisms (0.1 · 0.2 · 0.25 mm), data/parameters = 3960/
2
(No. 19),
1
1 1
˚
˚
˚
3
3
˚
260.1(8) A , Z = 4, D = 1.142 g/cm , T = 297 K, l =
.072 mm , k = 0.71073 A, F(000) = 856, light yellow
x
ꢂ1
˚
54; final R = 0.0446, wR = 0.1265 (all data).
1
2
(
m) Gennari, C.; Piarulli, U. Chem. Rev. 2003, 103, 3071–
+
4
.16.4.
Crystal
data
for
9a. [C H N O ]
3099; (n) Colacot, T. J. Chem. Rev. 2003, 103, 3101–3118;
(o) Desimoni, G.; Faita, G.; Quadrelli, P. Chem. Rev.
2003, 103, 3119–3154; (p) Chen, Y.; Yekta, S.; Yudin, A.
K. Chem. Rev. 2003, 103, 3155–3211; (q) Kocovsky, P.;
Vyskocil, S.; Smrcina, M. Chem. Rev. 2003, 103, 3213–
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3
7
51
2
2
ꢂ
Cl Æ2(H O), M = 626.27, trigonal, space group P3
2
1
˚ ˚
(
No. 144), a = 15.873(2) A, b = 15.873(2) A, c =
3
˚
˚
1
1
0
0
1.706(2) A, c = 120ꢁ, V = 2554.2(6) A , Z = 3, D =
x
3
ꢂ1
.222 g/cm ,
T = 297 K,
l = 0.153 mm
,
k =
˚
.71073 A, F(000) = 1017, light brown prisms (0.3 ·
3
247–3261; (s) Sibi, M. P.; Manyem, S.; Zimmerman, J.
.3 · 0.35 mm),
1
data/parameters = 5988/398;
final
Chem. Rev. 2003, 103, 3263–3295; (t) Walsh, P. J.; Lurain,
A. E.; Balsells, J. Chem. Rev. 2003, 103, 3297–3334; (u)
Faller, J. W.; Lavoie, A. R.; Parr, J. Chem. Rev. 2003, 103,
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R = 0.0595, wR = 0.1577 (all data).
2
Crystallographic data (excluding structural factors)
for the structures reported in this paper have been
deposited with the Cambridge Crystallographic Data
Centre and allocated the deposition numbers: CCDC
91395 for 6b, CCDC 291396 for 6e, CCDC 291397
for 7a, and CCDC 291398 for 9a. Copies of the data
can be obtained free of charge on application to CCDC,
2 Union Road, Cambridge CB2 1EW, UK (fax: Int
code +44 (1223) 336 033; e-mail: deposit@ccdc.
cam.ac.uk).
2
003, 103, 3369–3400.
2
. Aguado, G. P.; Alvarez-Larena, A.; Illa, O.; Moglioni, A.
G.; Ortufio, R. M. Tetrahedron: Asymmetry 2001, 12, 25–
2
8.
. Zhang, A.; Nie, J.; Khrimnian, A. Tetrahedron Lett. 2004,
5, 9401–9403.
2
3
4
4
. (a) Chen, Y.-J.; Lin, R.-X.; Chen, C. Tetrahedron:
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1