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Organic & Biomolecular Chemistry
DOI: 10.1039/C7OB01576C
ARTICLE
Journal Name
Experimental Methods
Conflict of interest
Catalyst
4 was synthesized as previously reported,Error! There are no conflicts of interest to declare.
5
c
1
Bookmark not defined. characterized by H NMR and found
to be in agreement with literature.
Acknowledgements
General Experimental Procedure
We gratefully acknowledge Department of Science and
Technology, New Delhi for financial support (Grants no. IFA-13
CH-95 and SB/FT/CS-183/2013).
For a typical reaction run, cyclohexanone (5mL, 48 mmol) was
added to proline-based catalyst (0.19 mmol) and stirred,
followed by addition of water (17.5mL) resulting into
suspension (For equilibrating conditions this mixture was
stirred overnight to ensure complete dissolution of catalyst in
cyclohexanone water mixture). p-Nitrobenzaldehyde (189mg,
Notes and references
1
(a) C. Girard and H. B. Kagan, Angew. Chem. Int. Ed., 1998,
37, 2922-2959. (b) T.Satyanarayana,S. Abraham and H. B.
Kagan, Angew. Chem. Int. Ed., 2009, 48, 456-494.
1
2
.25mmol) was added to the suspension and was stirred for
4h. Progress of reaction was monitored by thin layer
2
3
4
C. Puchot, O. Samuel, E.Duñach, S. Zhao, C. Agami and H. B.
Kagan, J. Am. Chem. Soc.,1986, 108, 2353-2357
B. List, R. A. Lerner and C. F. Barbas III, J. Am. Chem. Soc.,
chromatography (TLC). The reaction was quenched using
saturated NH Cl solution and product was extracted in ethyl
2
000, 122, 2395-2396.
4
(a) M. Mauksch, S. Wei, M.Freund, A. Zamfir and S. B.
Tsogoeva, Orig. Life Evol.Biosph., 2010, 40, 79-91. (b) S. B.
Tsogoeva, Chem. Commun., 2010, 46, 7662-7669.
(a) B. List, Synlett, 2001, 1675-1686. (b) K.Sakthivel, W. Notz,
T. Bui and C. F. Barbas III, J. Am. Chem. Soc., 2001, 123, 5260-
5267.
acetate. The extracted product was analyzed using HPLC. A
typical reaction under these conditions with an enantiopure
catalyst yielded 95% of product after 24h with high diastereo-
and enantioselectivity (89% and 97%). Purified products were
5
6
1
1
characterized by H NMR. H NMR(400 MHz, CDCl
J = 8.2 Hz, 2H), 7.51 (d, J = 8.3 Hz, 2H), 4.90 (d, J = 8.2 Hz, 1H),
.09 (s, 1H), 2.66 – 2.55 (m, 1H), 2.50 (d, J = 13.7 Hz, 1H), 2.37
3
) – δ 8.21 (d,
(a) G. K. Friestad and J. Qin, J. Am. Chem. Soc., 2001, 123
,
9
922-9923. (b) S. Bahmanyar and K. N. Houk, J. Am. Chem.
4
Soc., 2001, 123, 11273-11283. (c) L. Hoang, S. Bahmanyar, K.
N. Houk and B. List, J. Am. Chem. Soc., 2003, 125, 16-17.
(a) S. P. Mathew, H. Iwamura and D. G. Blackmond, Angew.
Chem. Int. Ed., 2004, 43, 3317-3321. (b) H. Iwamura, S.P.
(
(
m, J = 13.4, 6.1 Hz, 1H), 2.18 (s, 1H), 2.16 – 2.08 (m, 1H), 1.83
d, J = 12.5 Hz, 1H), 1.74 – 1.49 (m, 2H), 1.45 – 1.22 (m, 1H).
7
8
Mathew and D.G. Blackmond, J. Am. Chem. Soc., 2004, 126
,
Job-Plot Analysis for CR–4 complex
1
1770-11771.
(a) M. Klussmann, S. P. Mathew, H. Iwamura, D. H. Wells Jr.,
UV spectra were recorded on Shimadzu UV-vis
spectrophotometer (Model 2450). 344.5 µM aqueous stock
solution of CR was prepared. The total concentration of two
components (catalyst and dye) was kept constant at 20 µM.
Samples for UV-analysis were prepared by adding specified
amount of aqueous CR solution in required amount of catalyst
or emulsion. Absorption spectra were recorded at 25⁰C after
A. Armstrong and D. G. Blackmond, Angew. Chem. Int. Ed.,
2
006, 45, 7989-7992. (b) M. Klussmann, H. Iwamura, S. P.
Mathew, D. H. Wells Jr., U. Pandya, A. Armstrong and D. G.
Blackmond, Nature, 2006, 441, 621-623. (c) Y. Hayashi, M.
Matsuzawa, J. Yamaguchi, S. Yonehara, Y. Matsumoto, M.
Shoji, D. Hashizume and H. Koshino, Angew. Chem. Int. Ed.,
2006, 45, 4593-4597. (d) R. M. Kellogg, Angew. Chem. Int.
Ed., 2007, 46, 494-497.
9
1
C. J. Welch, Chirality, 2001, 13, 425-427
10 minutes of sample preparation. Job-plot was obtained by
0 (a) A. Córdova, M. Engqvist, I. Ibrahem, J. Casas and H.
Sunden, Chem. Commun., 2005, 2047-2049. (b) A. Córdova,
H. Sunden, Y. Xu, I. Ibrahem, W. Zou and M. Engqvist, Chem.
Eur. J., 2006, 12, 5446-5451.
plotting the differential absorbance ∆A (∆A =Aexp-Aobs) versus
molefraction of CR, whereAexp is the actual absorbance of CR
at given molefraction (in the absence of 4) whereas Aobs is
1
1
1
1 A. Bruckmann, B. Rodríguez and C. Bolm, CrystEngComm,
corresponding absorbance in the presence of 4.
2
009, 11, 404-407
2 P. Dziedzic, W. Zou, I. Ibrahem, H. Sundén and A.
Córdova,Tetrahedron.Lett.,2006, 47, 6657-6661.
CD Analysis
3 (a) N. E. Hamdouni, X. Companyó, R. Rios and A. Moyano,
Chem. Eur. J., 2010, 16, 1142-1148. (b) A. S. Demir and S.
Eymur, Tetrahedron: Asymmetry, 2010, 21, 405-409.
CD analysis was carried out on Jasco 815 spectropolarimeter.
CD spectra were recorded for CR emulsion aggregates,
emulsions with six different enantiopurity of catalyst were
analyzed. The stoichiometric ratio considered for CR emulsion
aggregate analysis was obtained from CR emulsion Job-plot.
Samples were prepared in similar manner as mentioned for UV
analysis; total concentration of two components (CR and
emulsion) in this case was kept constant at 40µM.
1
4 (a) H. Torii, M. Nakadai, K. Ishihara, S. Saito and H.
Yamamoto, Angew. Chem. Int. Ed., 2004, 43, 1983-1986. (b)
Y. Hayashi, T. Sumiya, J. Takahashi, H. Gotoh, T.
Urushimaand, M. Shoji, Angew. Chem. Int. Ed., 2006, 45
958-961. (c) N. Mase, Y. Nakai, N. Ohara, H. Yoda, K. Takabe,
F. Tanak and C. F. Barbas. III, J. Am. Chem. Soc., 2006, 128
34-735. (d) Y. Hayashi, S. Aratake, T. Okano, J. Takahashi, T.
,
,
7
Sumiya and M. Shoji, Angew.Chem., 2006, 118, 5653-5655;
Angew. Chem. Int. Ed., 2006, 45, 5527-5529.
1
5 (a) S. Aratake, T.Itoh, T. Okano, N. Nagae, T. Sumiya, M. Shoji
and Y. Hayashi, Chem. Eur. J., 2007, 13, 10246-10256. (b) L.
Zhong, Q. Gao, J. Gao, J. Xiao and C. Li, J. Catal., 2007, 250
,
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