10.1002/ejoc.201800485
European Journal of Organic Chemistry
FULL PAPER
[13] A. Kadlčíková, R. Hrdina, I. Valterová, M. Kotora, Adv. Synth. Catal.
2009, 351, 1279-1283.
Experimental Section
[14] R. Hrdina, F. Opekar, J. Roithová, M. Kotora, Chem. Commun. 2009,
2314-2316.
Experimental details can be found in the Supporting information section.
[15] a) K. Vlašaná, R. Hrdina, I. Valterová, M. Kotora, Eur. J. Org. Chem.
2010, 7040-7044; b) K. Vlašaná, R. Betík, I. Valterová, D. Nečas, M.
Kotora, Curr. Organocat. 2016, 3, 301-305.
Acknowledgements
[16] a) A. Kadlčíková, I. Valterová, L. Ducháčková, J. Roithová, M. Kotora,
Chem. Eur. J. 2010, 16, 9442-9445; b) A. V. Malkov, O. Kysilka, M.
Edgar, A. Kadlčíková, M. Kotora, P. Kočovský, P. Chem. Eur. J. 2011,
17, 7162-7166; c) F. Hessler, R. Betík, A. Kadlčíková, R. Belle, M.
Kotora, Eur. J. Org. Chem. 2014, 7245-7252.
This work was supported by Czech Science Foundation (grant
no. 17-07707S). P. K. is grateful to the Grant Agency of Charles
University (project No. 794216). The authors thank P. Kočovský
for useful comments during the preparation of the manuscript.
[17] a) ref. 9; b) V. A. Malkov, L. Dufková, L. Farrugia, P. Kočovský, Angew.
Chem. Int. Ed. 2003, 42, 3674-3677; c) A. V. Malkov, M. Bell, M.
Vassieu, V. Bugatti, P. Kočovský, J. Mol. Catal. A 2003, 196, 179-186;
d) A. V. Malkov, M. Bell, F. Casteluzzo, P. Kočovský, P. Org. Lett. 2005,
7, 3219-3222.
Keywords: chiral Lewis bases • organocatalysis • asymmetric
allylation • aldehydes • catalyst design
[18] R. Hrdina, I. G. Stará, L. Dufková, S. Mitchell, I. Císařová, M. Kotora,
Tetrahedron 2006, 62, 968-976; b) Q. Chai, C. Song, Z. Sun, Y. Ma, C.
Ma, Y. Dai, M. B. Andrus, Tetrahedron Lett. 2006, 47, 8611-8615; c) J.
R. Fulton, J. E. Glover, L. Kamara, G. J. Rowlands, Chem. Commun.
2011, 47, 433–435.
[1]
For reviews, see: (a) S. E. Denmark, J. Fu, Chem. Rev. 2003, 103,
2763-2793; b) A. V. Malkov, P. Kočovský, Eur. J. Org. Chem. 2007, 29-
36; c) P. Kočovský, A. V. Malkov, Pure Appl. Chem. 2008, 73, 953-966;
d) M. Yus, J.-C. González-Gómez, F. Foubelo, Chem. Rev. 2011, 111,
7774-7854; e) M. Yus, J.-C. González-Gómez, F. Foubelo, Chem. Rev.
2013, 113, 5595-5698; f) P. Kočovský, A. V. Malkov in Lewis Bases in
Comprehensive Enantioselective Organocatalysis (Ed. P. I. Dalko),
Wiley-VCH, Weinheim: 2013, vol 2, p. 381; g) A. V. Malkov, P.
Kočovský in Lewis-Base Catalyzed Reactions of SiX3-Based Reagents
with C=O, C=N (n*) in Lewis Base Catalysis in Organic Synthesis
(Eds E. Vedejs, S. E. Denmark.), Wiley-VCH: New York 2016, vol 2, p,
982.
[19] A. V. Malkov, M. Bell, F. Castelluzo, P. Kočovský, Org. Lett. 2005, 7,
1047-1049.
[20] Y. Naganawa, H. Abe, H. Nishiyama, Synlett 2016, 27, 1973-1978.
[21] A. Kadlčíková, M. Kotora, Molecules 2009, 14, 2918-2926.
[22] D. E. Denmark, Y. Fan, Tetrahedron: Asymmetry 2006, 17, 687-707.
For other applications in chiral N,N’-dioxide synthesis, see ref. 12.
[23] H. Friebolin, Basic One- and Two-Dimensional NMR Spectroscopy,
Wiley: Weinheim, 2005, 305.
[2]
[3]
a) M Fujii, A. Honda, J. Heterocyclic Chem. 1992, 29, 931-933; b) M
Fujii, A. Honda, Chem. Exp. 1992, 7, 329-332.
[24] P. Motloch, I. Valterová, M. Kotora, Adv. Synth. Catal. 2014, 356, 199-
204.
For a pioneering work on application of N,N’-dioxides as catalysts, see:
M. Nakajima, M. Saito, M. Shiro, S. Hashimoto, J. Am. Chem. Soc.
1998, 120, 6419-6420.
[25] P. Koukal, J. Ulč, D. Nečas, M. Kotora, M. Eur. J. Org. Chem. 2016,
2110-2114.
[26] E. Matoušová, P. Koukal, B. Formánek, M. Kotora, Org. Lett. 2016, 18,
5656-5659.
[4]
[5]
a) T. Shimada, A. Kina, S. Ikeda, T. Hayashi, Org. Lett. 2002, 4, 2799-
2801; b) A. Kina, T. Shimada, T. Hayashi, Adv. Synth. Catal. 2004, 349,
1169-1174.
[27] A. V. Malkov, P. Ramírez-López, L. Biedermannová, L. Rulíšek, L.
Dufková, M. Kotora, F. Zhu, P. Kočovský, J. Am. Chem. Soc. 2008, 130,
5341-5348.
a) R. Hrdina, A. Kadlčíková, I. Valterová, J. Hodačová, M. Kotora,
Tetrahedron: Asymmetry 2006, 17, 3185-3191; b) R. Hrdina, I.
Valterová, J. Hodačová, I. Císařová, M. Kotora, Adv. Synth. Catal. 2007,
349, 822-826; c) R. Hrdina, M. Dračínský, I. Valterová, J. Hodačová, I.
Císařová, M. Kotora, Adv. Synth. Catal. 2008, 350, 1449-1456; d) A.
Kadlčíková, R. Hrdina, I. Valterová, M. Kotora, Adv. Synth. Catal. 2009,
351, 1279-1283.
[28] For a seminal paper regarding dichotomy in the reaction mechanism of
allylation catalyzed by N-oxides, see: A. V. Malkov, S. Stončius, M. Bell,
F. Castelluzzo, P. Ramírez-López, L. Biedermannová, V. Langer, L.
Rulíšek, P. Kočovský, Chem. Eur. J. 2013, 19, 9167-9185.
[29] For further discussions on N,N’-dioxides properties, see: (a) L.
Ducháčková, A. Kadlčíková, M. Kotora, J. Roithová, J. Am. Chem. Soc.
2010, 132, 12660-12667; b) J. Váňa, J. Roithová, M. Kotora, P. Beran,
L. Rulíšek, P. Kočovský, Croat. Chem. Acta. 2014, 87, 347-355.
[30] D. Kost, I. Kalikhman, Acc. Chem. Res. 2009, 42, 303-314.
[31] For example, allylation of benzaldehyde catalyzed by (S)-5 proceeded
with 94% ee (see Table 4). For comparison, enantioselectivity of the
same reaction proceeded was 95% ee with 1j (1 mol%, CH2Cl2, -80 °C,
16 h),[7a] 92 and 96% ee with N-oxide catalysts such as PINDOX (10
mol%, CH2Cl2, -90 °C, 24 h)[9] and METHOX (10 mol%, CH2Cl2, -40 °C,
18 h),17d 93% ee with an aza-paracyclophane-oxazoline-N-oxide (1.5
mol%, 6 h, MeCN, -40 °C),[18b] and 98% ee with a bipyridine catalyst
derived from (+)-nopinone (7 mol%, CH2Cl2, -60 °C, 12 h).[9]
[32] a) T. Lu, R. Zhu, Y. An, S. E. Wheeler, J. Am. Chem. Soc. 2012, 134,
3095-3102; b) B. J. Rooks, M. R. Haas, D. Sepulveda, T. Lu, S. E.
Wheeler, ACS Catal. 2015, 5, 272-280.
[6]
[7]
J. Kwak, J. Ohk, Y. Jung, S. Chang, J. Am. Chem. Soc. 2012, 134,
17778-17788.
a) B. Bai, L. Shen, J. Ren, J.-H. Zhu, Adv. Synth. Catal. 2012, 354,
354–358; b) Y. Deng, W. Pan, N.-Y. Pei, L.-J. Li, B. Bai, J.-H. Zhu,
Tetrahedron 2013, 69, 10431-10437.
[8]
[9]
A. V. Malkov, M.-M. Westwater, A. Gutnov, P. Ramírez-López, F.
Friscourt, A. Kadlčíková, J. Hodačová, Z. Rankovic, M. Kotora, P.
Kočovský, Tetrahedron 2008, 64, 11335-11348.
A. V. Malkov, M. Orsini, D. Pernazza, W. K. Muir, V. Langer, P.
Meghani , P.; Kočovský, Org. Lett. 2002, 4, 1047-1049.
[10] a) L. Pignataro, M. Benaglia, M. Cinquini, F. Cozzi, G. Celentano,
Chirality 2005, 17, 396-403; b) G. Chelucci, N. Belmonte, M. Benaglia,
L. Pignataro, L. Tetrahedron Letters 2007, 48, 4037-4041.
[11] R. D. Boyd, D. N. Sharma, L. Sbircea, D. Murphy, F. J. Malone, L. S.
James, C. R. C. Allen, T. G. J. Hamilton, Org. Biomol. Chem. 2010, 8,
1081-1090.
[33] a) S. E. Wheeler, T. J. Seguin, Y. Guan, A. C. Doney, Acc. Chem. Res.
2016, 49, 1061-1069; b) T. Lu, S. E. Wheeler, Science 2016, 347, 719-
720.
[12] S. P. O´Hora, A. C. Incerti-Pradillos, A. M. Kabeshov, A. S.
Shipilovskikh, E. A. Rubtsov, R. J. M. Elsegood, A. V. Malkov, Chem.
Eur. J. 2015, 21, 4551-4555.
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