Angewandte Chemie International Edition
10.1002/anie.201708620
COMMUNICATION
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1
Stalke in Lithium Compounds in Organic Synthesis
–
From
Fundamentals to Applications (Eds.: R. Luisi, V. Capriati), Wiley VCH,
Weinheim, 2014, pp. 1-31.
[
10]
Figure 7. Lewis formula (left), asymmetric unit of 9 in the crystal (middle)
,
[
2]
a) U. Kroesen, L. Knauer, C. Strohmann, Angew. Chem. Int. Ed. 2017,
as well as extended coordination environment of the sodium centres and the
allyl moiety (right). Symmetry operations: #1 x, y1/2, z+1/2, #2 x,y+2,z,
3 x, y+1/2, z+1/2. Selected bond lengths [Å] and angles [°]: C1Na
.719(2), C2Na 2.749(2), C3Na 2.669(2), NNa 2.4622(17), NC1 1.445(3),
C1C2 1.373(3), C2C3 1.387(3), NC1Na 64.20(10), C1C2C3 131.0(2),
NC1C2 121.3(2).
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#
2
2
2
2
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Single crystals of the highly reactive intermediate could be
obtained (Figure 7). Compound 9 crystallized in the monoclinic
Beak, Angew. Chem. Int. Ed. 1998, 37, 2522-2524; i) D. D. Kim, S. J.
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1
crystal system in the space group P2 /c. The asymmetric unit
contains complete monomer of the solvent-free 2D
a
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coordination polymer. The sodium centre is intramolecularly
3
2
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coordinated in a η -mode by the cisoid allyl moiety.
2
The further reaction of 9 with electrophiles has been investigated.
First results show that only the γ-substituted product is formed
as it is the case when reacting the lithiated analogues of 2 and 3
with silanes. The ratio of the cis and trans isomers depends
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strongly
trimethylchlorosilane has a high favour of the cis-configured
product whereas trimethylchlorostannane has distinct
preference for the trans product. Additional investigations will be
performed in the future to clarify the preference of either the cis
or the trans isomer.
on
the
electrophile
used.
For
example,
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a
[5]
Within this paper the strong influence of the amine handle as
well as the metalating reagent, especially the alkali metal, on the
structure and reactivity of allylic amines could be shown.
Quantum chemical calculations deliver a good explanation for
the solvent independent selective carbometalation and
elimination for the allylic amine with only one coordinating
handle. In contrast, allylic amines with two or more
[
6]
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a) D. Enders, M. Klatt, Synthesis 1996, 1403-1421; b) J. O. Bauer, C.
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8102-8103.
[
[8]
Detailed information on the used theoretical methods see: V. H.
Gessner, S. G. Koller, C. Strohmann, A.-M. L. Hogan, D. F. O’Shea,
Chem. Eur. J. 2011, 17, 2996-3004.
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Strohfeldt, D. Schildbach, M. J. McGrath, P. O’Brien, Organometallics
intramolecular coordinating groups perform
a
selective
deprotonation. By isolating highly reactive intermediates the
structure of metalated allylic amines could be well described.
Also the sodiated structure shows clearly the influence of the
alkali metal. Using the sodium containing Schlosser’s base
instead of alkyl lithium reagents delivers a nice solution to
perform a deprotonation instead of a carbometalation of the
piperidine-substituted allylic amine. In the future, further
investigations on the formation of cis and trans substituted
products will be performed.
2004, 23, 5289-5391; c) M. Vestergren, J. Eriksson, G. Hilmersson, M.
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[10] CCDC 1569697, CCDC 1569698 and CCDC 1569699 contain the
supplementary crystallographic data for this paper. These data can be
the Supporting Information.
[
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4566-4569; b) T. Niklas, D. Stalke, M. John, Chem. Commun. 2015, 51,
1275-1277.
Keywords: allylic compounds • lithiation • structure-reactivity
relationships • X-ray diffraction • chemoselectivity
[12] C. Unkelbach, D. F. O’Shea, C. Strohmann, Angew. Chem. Int. Ed.
014, 53, 553-55.
2
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