-
1
-
-
55049138759
-
-
For recent reviews, see: a, Ed, P. I. Dalko, Wiley-VCH, Weinheim
-
For recent reviews, see: a) Enantioselective Organocatalysis (Ed.: P. I. Dalko), Wiley-VCH, Weinheim, 2007;
-
(2007)
Enantioselective Organocatalysis
-
-
-
4
-
-
52149113820
-
-
for a commentary on the advent of asymmetric organocatalysis, see: c
-
for a commentary on the advent of asymmetric organocatalysis, see: c) D. W. C. MacMillan, Nature 2008, 455, 304.
-
(2008)
Nature
, vol.455
, pp. 304
-
-
MacMillan, D.W.C.1
-
5
-
-
0034748990
-
-
For recent reviews on aminocatalysis, see: a
-
For recent reviews on aminocatalysis, see: a) B. List, Synlett 2001, 1687;
-
(2001)
Synlett
, pp. 1687
-
-
List, B.1
-
6
-
-
68349095644
-
-
P. Melchiorre, M. Marigo, A. Carlone, G.. Bartoli, Angew. Chem. 2008, 120, 6232;
-
b) P. Melchiorre, M. Marigo, A. Carlone, G.. Bartoli, Angew. Chem. 2008, 120, 6232;
-
-
-
-
8
-
-
38349100690
-
-
for a review on iminium catalysis, see: for a review on enamine catalysis, see: c
-
for a review on enamine catalysis, see: c) S. Mukherjee, J. W. Yang, S. Hoffmann, B. List, Chem. Rev. 2007, 107, 5471; for a review on iminium catalysis, see:
-
(2007)
Chem. Rev
, vol.107
, pp. 5471
-
-
Mukherjee, S.1
Yang, J.W.2
Hoffmann, S.3
List, B.4
-
9
-
-
33745715054
-
-
for a seminal paper on dienamine catalysis, see
-
d) G. Leiais, D.W.C. MacMillan, Aldrichimica Acta 2006, 39, 79; for a seminal paper on dienamine catalysis, see:
-
(2006)
Aldrichimica Acta
, vol.39
, pp. 79
-
-
Leiais, G.1
MacMillan, D.W.C.2
-
10
-
-
33749527371
-
-
for a seminal paper on organoSOMO catalysis, see
-
e) S. Bertelsen, M. Marigo, S. Brandes, P. Dinér, K. A. Jørgensen, J. Am. Chem. Soc. 2006, 128, 12973; for a seminal paper on organoSOMO catalysis, see:
-
(2006)
J. Am. Chem. Soc
, vol.128
, pp. 12973
-
-
Bertelsen, S.1
Marigo, M.2
Brandes, S.3
Dinér, P.4
Jørgensen, K.A.5
-
11
-
-
34247565955
-
-
f) T. D. Beeson, A. Mastracchio, J.-B. Hong, K. Ashton, D. W. C. MacMillan, Science 2007, 316, 582.
-
(2007)
Science
, vol.316
, pp. 582
-
-
Beeson, T.D.1
Mastracchio, A.2
Hong, J.-B.3
Ashton, K.4
MacMillan, D.W.C.5
-
15
-
-
0037419866
-
-
Only two examples of iminium-catalyzed conjugate addition of prochiral nucleophiles to enals with high diastereoselectivity (7 to 24:1 dr) have been reported: a) S. P. Brown, N. C. Goodwin, D. W. C. MacMillan, J. Am. Chem. Soc. 2003, 125, 1192;
-
Only two examples of iminium-catalyzed conjugate addition of prochiral nucleophiles to enals with high diastereoselectivity (7 to 24:1 dr) have been reported: a) S. P. Brown, N. C. Goodwin, D. W. C. MacMillan, J. Am. Chem. Soc. 2003, 125, 1192;
-
-
-
-
16
-
-
51749120761
-
-
for a different organocatalytic approach based on cinchona alkaloids, see
-
b) S. Cabrera, E. Reyes, J. Alema'n, A. Milelli, S. Kobbelgaard, K. A. Jørgensen, J. Am. Chem. Soc. 2008, 130, 12031; for a different organocatalytic approach based on cinchona alkaloids, see:
-
(2008)
J. Am. Chem. Soc
, vol.130
, pp. 12031
-
-
Cabrera, S.1
Reyes, E.2
Alema'n, J.3
Milelli, A.4
Kobbelgaard, S.5
Jørgensen, K.A.6
-
17
-
-
33845211302
-
-
c) F. Wu, R. Hong, J. Khan, J. Liu, L. Deng, Angew. Chem. 2006, 118, 4407;
-
(2006)
Angew. Chem
, vol.118
, pp. 4407
-
-
Wu, F.1
Hong, R.2
Khan, J.3
Liu, J.4
Deng, L.5
-
19
-
-
68349117739
-
-
For recent examples of low diastereoselective, albeit highly enantioselective, conjugate additions to enals promoted by III through ¡minium activation, see: a D. A. Alonso, S. Kitagaki, N. Utsumi, C. F. Barbas III, Angew. Chem. 2008, 120, 4664;
-
For recent examples of low diastereoselective, albeit highly enantioselective, conjugate additions to enals promoted by III through ¡minium activation, see: a) D. A. Alonso, S. Kitagaki, N. Utsumi, C. F. Barbas III, Angew. Chem. 2008, 120, 4664;
-
-
-
-
21
-
-
37249064645
-
-
b) H. Gotoh, H. Ishikawa, Y Hayashi, Org. Lett. 2007, 9, 5307.
-
(2007)
Org. Lett
, vol.9
, pp. 5307
-
-
Gotoh, H.1
Ishikawa, H.2
Hayashi, Y.3
-
22
-
-
1842732181
-
-
For different organocatalytic solutions, see, a
-
For different organocatalytic solutions, see : a) J. F. Austin, S.-G. Kim, C. J. Sinz, W.-J. J.iao, D. W. C MacMillan, Proc. Natl. Acad. Sci. USA 2004, 101, 5482;
-
(2004)
Proc. Natl. Acad. Sci. USA
, vol.101
, pp. 5482
-
-
Austin, J.F.1
Kim, S.-G.2
Sinz, C.J.3
iao, W.-J.J.4
MacMillan, D.W.C.5
-
23
-
-
18844451481
-
-
b) H. Li, Y. Wang, L. Tang, F. Wu, J. Liu, C. Guo, B. M. Foxman, L. Deng, Angew. Chem. 2005, 117, 107;
-
(2005)
Angew. Chem
, vol.117
, pp. 107
-
-
Li, H.1
Wang, Y.2
Tang, L.3
Wu, F.4
Liu, J.5
Guo, C.6
Foxman, B.M.7
Deng, L.8
-
25
-
-
36749038344
-
-
c) G. Bartoli, M. Bosco, A. Carlone, A. Cavalli, M. Locatelli, A Mazzanti, L. Sambri, P. Melchiorre, Angew. Chem. 2006, 118, 5088;
-
(2006)
Angew. Chem
, vol.118
, pp. 5088
-
-
Bartoli, G.1
Bosco, M.2
Carlone, A.3
Cavalli, A.4
Locatelli, M.5
Mazzanti, A.6
Sambri, L.7
Melchiorre, P.8
-
27
-
-
58249120495
-
-
For recent examples on the use of chiral primary amine thiourea catalysts in enamine activation, see, a
-
For recent examples on the use of chiral primary amine thiourea catalysts in enamine activation, see : a) D. A. Yalalov, S. B. Tsogoeva, T. E. Shubina, I. M. Martynova, T. Clark, Angew. Chem. 2008, 120, 6726;
-
(2008)
Angew. Chem
, vol.120
, pp. 6726
-
-
Yalalov, D.A.1
Tsogoeva, S.B.2
Shubina, T.E.3
Martynova, I.M.4
Clark, T.5
-
31
-
-
34250619640
-
-
d) M. P. Lalonde, Y Chen, E. N. Jacobsen, Angew. Chem. 2006, 118, 6514;
-
(2006)
Angew. Chem
, vol.118
, pp. 6514
-
-
Lalonde, M.P.1
Chen, Y.2
Jacobsen, E.N.3
-
33
-
-
33947389167
-
-
e) S. Luo, H. Xu, J. Li. L. Zhang, J.-P. Cheng, J. Am. Chem. Soc. 2007, 129, 3074;
-
(2007)
J. Am. Chem. Soc
, vol.129
, pp. 3074
-
-
Luo, S.1
Xu, H.2
Zhang, J.L.L.3
Cheng, J.-P.4
-
35
-
-
53849084173
-
-
For recent cinchona alkaloid catalyzed asymmetric aldol-type reactions of oxindoles, providing contiguous quaternary stereocenters, see: a
-
For recent cinchona alkaloid catalyzed asymmetric aldol-type reactions of oxindoles, providing contiguous quaternary stereocenters, see: a) S. Ogawa, N. Shibata, J. Inagaki, S. Nakamura, T. Toru, M. Shiro, Angew. Chem. 2007, 119, 8820;
-
(2007)
Angew. Chem
, vol.119
, pp. 8820
-
-
Ogawa, S.1
Shibata, N.2
Inagaki, J.3
Nakamura, S.4
Toru, T.5
Shiro, M.6
-
36
-
-
36549020091
-
-
8666; for asymmetric catalytic transformations by using oxindoles as the nucleophile, see
-
Angew. Chem. Int. Ed. 2007, 46, 8666; for asymmetric catalytic transformations by using oxindoles as the nucleophile, see:
-
(2007)
Angew. Chem. Int. Ed
, vol.46
-
-
-
37
-
-
44449174208
-
-
b) D. Sano, K. Nagata, T. Itoh, Org. Lett. 2008, 10, 1593;
-
(2008)
Org. Lett
, vol.10
, pp. 1593
-
-
Sano, D.1
Nagata, K.2
Itoh, T.3
-
38
-
-
53849116872
-
-
c) T. Ishimaru, N. Shibata, T. Horikawa, N. Yasuda, S. Nakamura, T. Toru, M. Shiro, Angew. Chem 2008, 120, 4225;
-
(2008)
Angew. Chem
, vol.120
, pp. 4225
-
-
Ishimaru, T.1
Shibata, N.2
Horikawa, T.3
Yasuda, N.4
Nakamura, S.5
Toru, T.6
Shiro, M.7
-
41
-
-
54049101193
-
-
e) X. Tian, K. Jiang, J. Peng, W. Du, Y.-C. Chen, Org. Lett. 2008, 10, 3583.
-
(2008)
Org. Lett
, vol.10
, pp. 3583
-
-
Tian, X.1
Jiang, K.2
Peng, J.3
Du, W.4
Chen, Y.-C.5
-
44
-
-
0038287938
-
-
and references therein;
-
c) A. B. Dounay, K. Hatanaka, J. J. Kodanko, M. Oestreich, L. E. Overman, L. A. Pfeifer, M. M. Weiss, J. Am. Chem. Soc. 2003, 125, 6261, and references therein;
-
(2003)
J. Am. Chem. Soc
, vol.125
, pp. 6261
-
-
Dounay, A.B.1
Hatanaka, K.2
Kodanko, J.J.3
Oestreich, M.4
Overman, L.E.5
Pfeifer, L.A.6
Weiss, M.M.7
-
49
-
-
10344242467
-
-
f) M. M. C. Lo, C S. Neumann, S. Nagayama, E. O. Perlstein, S. L. Schreiber, J. Am. Chem. Soc. 2004, 126, 16077.
-
(2004)
J. Am. Chem. Soc
, vol.126
, pp. 16077
-
-
Lo, M.M.C.1
Neumann, C.S.2
Nagayama, S.3
Perlstein, E.O.4
Schreiber, S.L.5
-
50
-
-
68349115450
-
-
For meaningful examples of the potential of chiral primary amines derived from cinchona alkaloids in iminium activation of enones, see: a J.-W. Xie, W. Chen, R. Li, M. Zeng, W. Du, L. Yue, Y.-C. Chen, Y. Wu, J. Zhu, J.-G. Deng, Angew. Chem. 2007, 119, 393;
-
For meaningful examples of the potential of chiral primary amines derived from cinchona alkaloids in iminium activation of enones, see: a) J.-W. Xie, W. Chen, R. Li, M. Zeng, W. Du, L. Yue, Y.-C. Chen, Y. Wu, J. Zhu, J.-G. Deng, Angew. Chem. 2007, 119, 393;
-
-
-
-
52
-
-
38549098664
-
-
b) W. Chen, W. Du, Y.-Z. Duan, Y. Wu, S.-Y. Yang, Y.-C. Chen, Angew. Chem. 2007, 119, 7811;
-
(2007)
Angew. Chem
, vol.119
, pp. 7811
-
-
Chen, W.1
Du, W.2
Duan, Y.-Z.3
Wu, Y.4
Yang, S.-Y.5
Chen, Y.-C.6
-
54
-
-
39749116151
-
-
c) R. P. Singh, K. Bartelson, Y. Wang, H. Su, X. Lu, L. Deng, J. Am. Chem. Soc. 2008, 130, 2422;
-
(2008)
J. Am. Chem. Soc
, vol.130
, pp. 2422
-
-
Singh, R.P.1
Bartelson, K.2
Wang, Y.3
Su, H.4
Lu, X.5
Deng, L.6
-
55
-
-
43249111803
-
-
d) X. Wang, C.M. Reisinger, B. List, J. Am. Chem. Soc. 2008, 130, 6070;
-
(2008)
J. Am. Chem. Soc
, vol.130
, pp. 6070
-
-
Wang, X.1
Reisinger, C.M.2
List, B.3
-
56
-
-
34147174295
-
-
e) G. Bartoli, M. Bosco, A. Carlone, F. Pesciaioli, L. Sambri, P. Melchiorre, Org. Lett. 2007, 9, 1403;
-
(2007)
Org. Lett
, vol.9
, pp. 1403
-
-
Bartoli, G.1
Bosco, M.2
Carlone, A.3
Pesciaioli, F.4
Sambri, L.5
Melchiorre, P.6
-
57
-
-
68349120860
-
-
f) F. Pesciaioli, F. De Vincentiis, P. Galzerano, G. Bencivenni, G. Bartoli, A. Mazzanti, P. Melchiorre, Angew. Chem. 2008, 120, 8831;
-
(2008)
Angew. Chem
, vol.120
, pp. 8831
-
-
Pesciaioli, F.1
De Vincentiis, F.2
Galzerano, P.3
Bencivenni, G.4
Bartoli, G.5
Mazzanti, A.6
Melchiorre, P.7
-
58
-
-
55249110210
-
-
for recent reviews, see
-
Angew. Chem. Int. Ed. 2008, 47, 8703; for recent reviews, see:
-
(2008)
Angew. Chem. Int. Ed
, vol.47
, pp. 8703
-
-
-
61
-
-
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-
-
To the best of our knowledge, chiral primary amines have not yet been used for the iminium activation of α,ß-unsaturated aldehydes; they have proven to be effective for the iminium activation of enones (see reference [10]) and of α-substituted acroleins, see: a) K. Ishihara, K. Nakano, J. Am. Chem. Soc. 2005, 127, 10504;
-
To the best of our knowledge, chiral primary amines have not yet been used for the iminium activation of α,ß-unsaturated aldehydes; they have proven to be effective for the iminium activation of enones (see reference [10]) and of α-substituted acroleins, see: a) K. Ishihara, K. Nakano, J. Am. Chem. Soc. 2005, 127, 10504;
-
-
-
-
62
-
-
33745725832
-
-
b) A. Sakakura, K. Suzuki, K. Nakano, K. Ishihara, Org. Lett. 2006, 8, 2229;
-
(2006)
Org. Lett
, vol.8
, pp. 2229
-
-
Sakakura, A.1
Suzuki, K.2
Nakano, K.3
Ishihara, K.4
-
64
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68349108975
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Both enantiomers of Via are easily accessible from a single-step synthesis, see the Supporting Information.
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Both enantiomers of Via are easily accessible from a single-step synthesis, see the Supporting Information.
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65
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68349106245
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It is likely that the acid serves to facilitate catalyst turnover by promoting iminium formation/imine hydrolysis; for similar effects with primary amine thiourea catalysts in enamine catalysis, see references [7b, c
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It is likely that the acid serves to facilitate catalyst turnover by promoting iminium formation/imine hydrolysis; for similar effects with primary amine thiourea catalysts in enamine catalysis, see references [7b, c].
-
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66
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68349113100
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2 = Cl) led to a decreased stereoselectivity in the reaction with 2a (1.5:1 dr; 11 % ee).
-
2 = Cl) led to a decreased stereoselectivity in the reaction with 2a (1.5:1 dr; 11 % ee).
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67
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84877935319
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These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
-
CCDC-710802 (4) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data-request/cif
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CCDC-710802 (4) contains the supplementary crystallographic data for this paper
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68
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2) in the catalyst scaffold led to a complete loss of catalytic activity and this evidence ruled out possible activation of the nucleophile through chiral Brønsted base catalysis.
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2) in the catalyst scaffold led to a complete loss of catalytic activity and this evidence ruled out possible activation of the nucleophile through chiral Brønsted base catalysis.
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69
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68349096769
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The employment of the N-Boc protected oxindole under the best reaction conditions afforded low stereocontrol, albeit with improved reactivity (18 h; >95% conversion; 2:1 dr; 67% ee).
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The employment of the N-Boc protected oxindole under the best reaction conditions afforded low stereocontrol, albeit with improved reactivity (18 h; >95% conversion; 2:1 dr; 67% ee).
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70
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68349110110
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The presence of the primary amine is crucial for the catalytic activity, see reference [16]; at this stage of the investigations a plausible Brønsted acid activation of unsaturated aldehydes cannot be ruled out.
-
The presence of the primary amine is crucial for the catalytic activity, see reference [16]; at this stage of the investigations a plausible Brønsted acid activation of unsaturated aldehydes cannot be ruled out.
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