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3142753716
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and references cited therein
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17444374300
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and references cited therein
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43
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7044272565
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Benaglia, M.1
Negri, D.2
Dell'Anna, G.3
-
44
-
-
22244487956
-
-
We have recently found that the arylacetylene addition to imines is promoted also by chiral diamine/Cu(I) complexes. See: Orlandi, S.; Colombo, F.; Benaglia, M. Synthesis 2005, 1689-1691. The bisimine/Cu(I) catalysts usually performed better than diamine/Cu(I) complexes in terms of yields and stereoselectivities.
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(2005)
Synthesis
, pp. 1689-1691
-
-
Orlandi, S.1
Colombo, F.2
Benaglia, M.3
-
45
-
-
0034624411
-
-
Reetz, M. T.; Haderlein, G.; Angermund, K. J. Am. Chem. Soc. 2000, 122, 996. Following the reported procedure, in our hands, product 9 was obtained in 51% yield after chromatographic purification.
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J. Am. Chem. Soc.
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-
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Reetz, M.T.1
Haderlein, G.2
Angermund, K.3
-
46
-
-
33644641615
-
-
note
-
The use of other, even more hindered, ligands like a chiral bisimine derived from 2-hydroxy-3-t-butyl-benzaldehyde did not allow the improvement of the enantioselectivity, which was always in a 70-80% ee range. See also ref 29.
-
-
-
-
47
-
-
33644655071
-
-
manuscript in preparation
-
On the contrary, in a chiral bisimine/metal catalyzed allylation of imines, we have recently discovered a positive effect of the thiophene ring on the stereoselectivity of the process. See: Colombo, F.; Benaglia, M.; Cozzi, F.; Cinquini, M. manuscript in preparation.
-
-
-
Colombo, F.1
Benaglia, M.2
Cozzi, F.3
Cinquini, M.4
-
48
-
-
33644642791
-
-
note
-
In the case of product 11, it was possible to obtain a basically enantiomerically pure compound after a single crystallization step even starting from a sample with 65% ee.
-
-
-
-
49
-
-
33644647584
-
-
note
-
Other ligands were less efficient; for example, with ligand 1, after 48 h, less than 60% conversion was observed. Furthermore, because with other substrates and different acetylenic reagents different reaction rates were observed, for the sake of comparison, a 72 h reaction time was kept in all the experiments.
-
-
-
-
50
-
-
33644660336
-
-
note
-
At 0 °C, other ligands, like 2, 5, and 6, did not promote the reaction at all.
-
-
-
-
51
-
-
33644651684
-
-
note
-
11 do use CuBr as the Cu(I) source, but it is complexed with Quinap or other related biaryl P,N ligands, and the reaction is believed to proceed through a different mechanism that involves an enamine formation.
-
-
-
-
52
-
-
33644647732
-
-
note
-
Any attempt to obtain crystals of the chiral bisimine/copper(I) complex was unsuccessful. For the proposed reaction mechanism, we do have NMR evidence of Cu(I)-imine coordination. Then the formation of a Cu-alkynide, as suggested by one of the referees, is a possibility. However, on the basis of our own investigation, at the moment we are not in the position to indicate the structure of the real active catalytic species and to assign the geometry at the copper ion.
-
-
-
-
53
-
-
33644654704
-
-
note
-
Imines derived from heteroaromatic aldehydes reacted sluggishly and with low enantioselectivity; imines derived from cinnamic aldehyde and aliphatic aldehydes did not react at all, as well as N-alkyl imines. N-phenyl imine of ethylglyoxalate was completely consumed after only 12 h of reaction, but any attempt to isolate a well-defined product was unsuccessful.
-
-
-
-
54
-
-
33644656490
-
-
note
-
For the degradation of N-2-methoxyphenyl anilines, see ref 7.
-
-
-
-
55
-
-
33644661230
-
-
note
-
2). These results match with those reported in the recent paper by Li et al. (ref 8), where the absolute configuration of N-[1-(3-bromophenyl)-3-phenyl-2- propynyl]-aniline was determined by X-ray crystallography.
-
-
-
-
56
-
-
33644655621
-
-
note
-
Only very recently have alkylacetylenes been employed in a direct addition to imines (see ref 8). For other examples of the use of alkylacetylenes in other methodologies, see refs 9 and 7.
-
-
-
-
58
-
-
33644662217
-
-
submitted
-
An asymmetric, multicomponent, copper-catalyzed synthesis of chiral propargylamines was developed. See: Colombo, F.; Benaglia, M.; Orlandi, S.; Usuelli, F. J. Mol. Catal. A: Chem. 2005, submitted.
-
(2005)
J. Mol. Catal. A: Chem.
-
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Colombo, F.1
Benaglia, M.2
Orlandi, S.3
Usuelli, F.4
-
59
-
-
33644658439
-
-
note
-
The enantiomerically enriched propargylamines 11, 21-29, 35-39, and 41-44 all showed positive optical rotation values.
-
-
-
-
60
-
-
0034612944
-
-
Kodama, H.; Taji, T.; Ohta, T.; Furukawa, I. Tetrahedron: Asymmetry 2000, 11, 4009.
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(2000)
Tetrahedron: Asymmetry
, vol.11
, pp. 4009
-
-
Kodama, H.1
Taji, T.2
Ohta, T.3
Furukawa, I.4
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