An easy synthesis of some 1,2,3,4-tetrahydro-9-oxa-10-phospha-phenanthrene-10-oxides

Article abstract of DOI:10.1081/SCC-100000195

2-Cycloalkenylphenols 3 react under mild conditions with PCl₃ to give the 10-chloro-2,3,4,10-tetrahydro-1H-9-oxa-10-phospha-phenanthrenes 4. The latter are readily hydrolyzed to afford the 1,2,3,4-tetrahydro-9-oxa-10-phospha-phenanthrene-10-oxi

Full text of DOI:10.1081/SCC-100000195

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AN EASY SYNTHESIS OF SOME 1,2,3,4-
TETRAHYDRO-9-OXA-10-PHOSPHA-
PHENANTHRENE-10-OXIDES
Peter Nesvadba & Paul Dubs
Published online: 16 Aug 2006.
To cite this article: Peter Nesvadba & Paul Dubs (2001) AN EASY SYNTHESIS OF SOME 1,2,3,4-TETRAHYDRO-9-OXA-10-
PHOSPHA-PHENANTHRENE-10-OXIDES, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 31:2, 161-165, DOI: 10.1081/SCC-100000195
To link to this article: http://dx.doi.org/10.1081/SCC-100000195
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SYNTHETIC COMMUNICATIONS, 31(2), 273–277 (2001)
YTTERBIUM METAL/TMSCL PROMOTED
REACTION OF IMINES WITH
ALLYLIC BROMIDE
Weike Su,1,2 Jinghua Li,1 and Yongmin Zhang2,∗
1Department of Pharmaceutical Engineering, Zhejiang University
of Technology, Hangzhou, 310014, P.R. China
2Department of Chemistry, Zhejiang University at Xixi Campus, Hangzhou,
310028, P.R. China
ABSTRACT
In the presence of chlorotrimethylsilane (TMSCl), ytterbium
metal can promote the allylation of imines with allylic bromide to
give the corresponding homoallylamines in satisfactory yields in
THF under mild conditions.
An important method for preparing secondary amines is the addition of
carbon nucleophiles to the carbon-nitrogen double bound in imines. Generally,
allylmetallic halides are used as carbon nucleophiles. Among these, those that
can be used for allylation of imines include allylmagnesium (1), allylzinc (2),
allystannane (3,4), allyl lead (5), allyltitanium (6), allylcopper (7), allylchrominum
(8), and allylsamarium (9). In some cases, metals have been directly employed for
promoting the allylation of imines, for example, tin (10), indium (11), bismuth,
and tantalum (12).
∗ To whom correspondence should be addressed.
273
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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SU, LI, AND ZHANG
Here we wish to report the allylation of imines with allylic bromide promoted
by Yb/TMSCl system.
Rapid developments of application of lanthanides, especially samarium
reagents, in organic synthesis have been recently achieved (13). However, rela-
tively few papers on ytterbium reagents have been reported. Nevertheless, there
are indications that ytterbium reagents, too, have the potential to serve as selec-
tive nucleophiles in C-X π-bond addition reactions, and eventually will take their
place among the other lanthanide reagents with a unique role in organic synthe-
sis. For example, ytterbium trifluoromethanesulfonate complexes can substitute
for traditional Lewis acids in a variety of organic transformations (14). Ytterbium
metal can selectively reduce C-C multiple bonds conjugated with aromatic rings
(15). PhYbI reacts with carbon dioxide to form carboxylic acid (16), with aldehy-
des and ketones to provide corresponding alcohols (17–19); with carboxylic acid
derivatives to provide ketones (20,21). Ytterbium diiodide promotes Barbier-type
reactions (22). But no reports on the direct use of ytterbium metal to promote the
allylation of imines with allylic bromide could be found.
In our experimental work, we found that ytterbium metal not only does not
react with allylic bromide to form allylytterbium bromide as does samarium, but
also does not promote the allylation of imines with allylic bromide directly. But
surprisingly, in the presence of TMSCl, ytterbium can promote the allylation of
imines with allylic bromide to give the corresponding homoallylamines easily. The
notable advantages of this methodology are mild conditions, simple operation, and
satisfactory yields. The results are summarized in Table 1.
Table 1. Ytterbium/TMSCl Promotes the Allylation of Imines
1
2
3
==
(R R C NR ) with Allylic Bromide
Run
R1
R2
R3
Yield∗ (%)
1
2
3
4
5
6
7
8
C6H5
C6H5
p-CH3OC6H4
2-Furyl
C6H5
p-ClC6H4
C6H5
C6H5
H
H
H
H
H
H
H
H
C6H5
p-BrC6H4
C6H5
C6H5
1-Naphthyl
C6H5
75
72
76
73
79
80
68
67
C6H5CHCH3
p-CH3OC6H4
∗Yields of isolated products.

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ALLYLATION OF IMINES
275
EXPERIMENTAL
1H-NMR spectra were recorded on Bruker AC-80 spectrometer using TMS
as internal standard. IR spectra were obtained on a PE-683 spectrometer. Tetrahy-
drofuran was freshly distilled from sodium benzophenone ketyl.
General Procedure for the Allylation of Imines
Ytterbium powder (0.173 g, 1 mmol), 5 mL of THF, and 0.121 g (1 mmol) of
allylic bromide (freshly distilled) were added to a three-necked flask under nitrogen
atmosphere. The mixture was magnetically stirred for 10 min at room temperature.
Then a solution of imine (1 mmol) in 2 mL of THFand a catalytic amount of TMSCl
was added to this suspension in one portion by syringe. The mixture was stirred
for 3–4 h at room temperature until the ytterbium powder disappeared. A dilute
solution of NaHCO3 (0.2 N, 20 mL) was added. The mixture was stirred for 10 min
and extracted with ether (20 mL × 2). The combined organic layer was washed with
brine (20 mL × 2) and dried over anhydrous Na2SO4. The solvent was removed
under reduced pressure. The crude product was purified by preparative TLC on
silica gel (cyclohexane and ethyl acetate as eluent). The products were identified
by IR and 1H-NMR spectra.
1: Oil (9), IR (Film, νmax, cm−1): 3250, 1650, 1600, 750, 730, 700; 1H-NMR
(CCl4), δ (ppm): 1.84 (s, 1H, NH), 2.18–2.70 (m, 2H, CH2), 4.06–4.50
(m, 1H, CH), 4.80–5.85 (m, 3H, vinyl-H), 6.00–7.30 (m, 10H, ArH).
1
2: Oil (9), IR (Film, νmax, cm−1): 3235, 1660, 1590, 760, 730, 695; H-
NMR (CCl4), δ (ppm): 1.85 (s, 1H, NH), 2.20–2.70 (m, 2H, CH2), 3.96
(t, J = 7.5 Hz, 1H, CH), 4.90–5.90 (m, 3H, vinyl-H), 6.00–7.27 (m, 9H,
ArH).
1
3: Oil (9), IR (Film, νmax, cm−1): 3205, 1645, 1600, 770, 690; H-NMR
(CCl4), δ (ppm): 1.84 (s, 1H, NH), 2.40 (t, J = 9.3 Hz, 2H, CH2), 3.60 (s,
3H, CH3O), 4.20 (t, J = 6.8 Hz, 1H, CH), 4.80–5.95 (m, 3H, vinyl-H),
6.05–7.25 (m, 9H, ArH).
1
4: Oil (11), IR (Film, νmax, cm−1): 3265, 1650, 1600, 755, 730, 605; H-
NMR (CCl4), δ (ppm): 1.84 (s, 1H, NH), 2.20–2.80 (m, 2H, CH2), 4.15–
4.50 (m, 1H, CH), 4.70–5.80 (m, 3H, vinyl-H), 6.15–7.20
(m, 8H, ArH).
1
5: Oil (10), IR (Film, νmax, cm−1): 3245, 1655, 1605, 755, 740, 700; H-
NMR (CCl4), δ (ppm): 1.83 (s, 1H, NH), 2.26–2.80 (m, 2H, CH2), 4.16–
4.60 (m, 1H, CH), 4.88–5.80 (m, 3H, vinyl-H), 6.30–6.68 (m, 12H, ArH).
1
6: Oil (9), IR (Film, νmax, cm−1): 3235, 1640, 1600, 750, 730, 695; H-
NMR (CCl4), δ (ppm): 1.94 (s, 1H, NH), 2.35 (t, J = 8.5 Hz, 2H, CH2),

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SU, LI, AND ZHANG
4.20 (t, J = 7.8 Hz, 1H, CH), 4.80–5.78 (m, 3H, vinyl-H), 6.20–7.30
(m, 9H, ArH).
7: Oil (10), IR (Film, νmax, cm−1): 3255, 3035, 1640, 1600, 755, 695;
1H-NMR (CCl4), δ (ppm): 1.25 (d, J = 8.0 Hz, 3H, CH3), 1.80
(s, 1H, NH), 2.30–2.70 (m, 2H, CH2), 3.50 (t, J = 7.1 Hz 1H, CH);
3.60–4.00 (m, 1H, CH), 5.00–5.80 (m, 3H, vinyl-H), 6.50–7.50 (m, 10H,
ArH).
1
8: Oil (8), IR (Film, νmax, cm−1): 3245, 1645, 1600, 765, 700; H-NMR
(CCl4), δ (ppm): 1.85 (s, 1H, NH), 2.57 (t, J = 9.0 Hz, 2H, CH2), 3.70 (s,
3H, CH3O), 4.15 (t, J = 8.5 Hz, 1H, CH), 5.00–5.85 (m, 3H, vinyl-H),
6.30–7.25 (m, 9H, ArH).
ACKNOWLEDGMENTS
We are grateful to the National Nature Science Foundation of China (project
No. 29872010), the NSF of Zhejiang province, China, and the Laboratory of
Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Science for financial support.
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Received in the UK October 21, 1999

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