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(4) Biological studies on DYCMs, see: (a) Takahashi, H.; Wakamatsu, S.; Tabata, H.; Oshitari, T.; Harada, A.; Inoue, K.; Natsugari,
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J.; Miike, T.; Shirahase, H.; Oshitari, T.; Takahashi, H.; Natsugari, H.,
Active Conformation of Seven-membered-ring Benzolactams as
New ACAT Inhibitors: Latent Chirality at N5 in the 1,5-Benzodiazepin-2-one Nucleus. Chem. Eur. J. 2012, 18, 1572-1576. (c) Selness,
S. R.; Devraj, R. V.; Devadas, B.; Walker, J. K.; Boehm, T. L.; Durley, R.
C.; Shieh, H.; Xing, L.; Rucker, P. V.; Jerome, K. D.; Benson, A. G.; Marrufo, L. D.; Madsen, H. M.; Hitchcock, J.; Owen, T. J.; Christie, L.;
Promo, M. A.; Hickory, B. S.; Alvira, E.; Naing, W.; Blevis-Bal, R.;
Messing, D.; Yang, J.; Mao, M. K.; Yalamanchili, G.; Embse, R. V.;
Hirsch, J.; Saabye, M.; Bonar, S.; Webb, E.; Anderson, G.; Monahan, J.
B., Discovery of PH-797804, a Highly Selective and Potent Inhibitor
of p38 MAP Kinase. Bioorg. Med. Chem. Lett. 2011, 21, 4066-4071.
(d) Wakamatsu, S.; Takahashi, Y.; Tabata, H.; Oshitari, T.; Tani, N.;
Azumaya, I.; Katsumoto, Y.; Tanaka, T.; Hosoi, S.; Natsugari, H.;
Takahashi, H., Conformation and Atropisomeric Properties of Indometacin Derivatives. Chem. Eur. J. 2013, 19, 7056-7063. (e)
Sugane, T.; Tobe, T.; Hamaguchi, W.; Shimada, I.; Maeno, K.; Miyata,
J.; Suzuki, T.; Kimizuka, T.; Sakamoto, S.; Tsukamoto, S.-I., Atropisomeric 4-Phenyl-4H-1,2,4-triazoles as Selective Glycine Transporter
1 Inhibitors. J. Med. Chem. 2013, 56, 5744-5756. For representative
reviews on biological studies on DYCMs, see (f) Clayden, J.; Moran,
W. J.; Edwards, P. J.; LaPlante, S. R., The Challenge of Atropisomerism in Drug Discovery. Angew. Chem. Int. Ed. 2009, 48, 6398-6401.
(g) Glunz, P. W., Recent Encounters with Atropisomerism in Drug
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(5) Recently, we have developed dynamic asymmetric induction
(DYASIN) of DYCMs, which provides optically active DYCMs by interaction with outer chiral source, see: Igawa, K.; Kawasaki, Y.; Ano,
Y.; Kashiwagi, T.; Ogawa, K.; Hayashi, J.; Morita, R.; Yoshioka, Y.;
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(6) For representative reviews on microflow reactors, see: (a)
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(7) For a review on dynamic NMR spectroscopy and dynamic
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(8) For a review on chiral HPLC analysis, see: Okamoto, Y.; Ikai,
T., Chiral HPLC for Efficient Resolution of Enantiomers. Chem. Soc.
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(9) The values of half-live of optical activity were calculated by
Eyring equation on the assumption that transmission coefficient is
one.
(10) Uncertainty of activation parameters owing to the narrow
thermal range of measurement was well discussed, see: Espenson,
J. H. Chemical Kinetics and Reaction Mechanisms, 2nd ed; McGrawHill, Inc.: New York, 1995.
(11) (a) Tomooka, K.; Iso, C.; Uehara, K.; Suzuki, M.; NishikawaShimono, R.; Igawa, K., Planar-chiral [7]Orthocyclophanes. Angew.
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Noguchi, K.; Uehara, K.; Tomooka, K., Synthesis and Stereochemical
Analysis of Planar-chiral (E)-4-[7]Orthocyclophene. J. Org. Chem.
2016, 81, 11587-11593.
(12) For representative studies on axial-chiral N-arylamides,
see: (a) Curran, D. P.; Qi, H. Y.; Geib, S. J.; Demello, N. C., Atroposelective Thermal-Reactions of Axially Twisted Amides and Imides. J.
Am. Chem. Soc. 1994, 116, 3131-3132. (b) Hughes, A. D.; Price, D.
A.; Shishkin, O.; Simpkins, N. S., Diastereoselective Enolate Chemistry using Atropisomeric Amides. Tetrahedron Lett. 1996, 37, 76077610. (c) Kitagawa, O.; Izawa, H.; Taguchi, T.; Shiro, M., An Efficient
Synthesis of Optically Active Axially Chiral Anilide and Its Application to Iodine-mediated Asymmetric Diels-Alder Reaction. Tetrahedron Lett. 1997, 38. 4447-4450. (d) Curran, D. P.; Liu, W. D.; Chen,
C. H. T., Transfer of Chirality in Radical Cyclizations. Cyclization of
o-Haloacrylanilides to Oxindoles with Transfer of Axial Chirality to
a Newly Formed Stereocenter. J. Am. Chem. Soc. 1999, 121, 1101211013. (e) Clayden, J.; McCarthy, C.; Helliwell, M., Bonded Peri-interactions Govern the Rate of Racemisation of Atropisomeric 8Substituted 1-Naphthamides. Chem. Commun. 1999, 2059-2060.
(f) Adler, T.; Bonjoch, J.; Clayden, J. Font-Bardía, M.; Pickworth, M.;
Solans, X.; Solé, D.; Vallverdú, L., Slow Interconversion of Enantiomeric Conformers or Atropisomers of Anilide and Urea Derivatives
of 2-Substituted Anilines. Org. Biomol. Chem. 2005, 3, 3173-3183.
(g) Guthrie, D. B.; Curran, D. P., Asymmetric Radical and Anionic Cyclizations of Axially Chiral Carbamates. Org. Lett. 2009, 11, 249251. (h) Shirakawa, S.; Liu, K.; Maruoka, K., Catalytic Asymmetric
Synthesis of Axially Chiral o-lodoanilides by Phase-transfer Catalyzed Alkylations. J. Am. Chem. Soc. 2012, 134, 916-919. (i) Nakazaki, A.; Miyagawa, K.; Miyata, N.; Nishikawa, T., Synthesis of a C-N
Axially Chiral N-Arylisatin through Asymmetric Intramolecular NArylation. Eur. J. Org. Chem. 2015, 4603-4606.
(13) Asano, S.; Takahashi, Y.; Maki, T.; Muranaka, Y.; Cherkasov,
N.; Mae, K., Contactless Mass Transfer for Intra-droplet Extraction.
Sci. Rep. 2020, 10, 7685. The developed software in this work can
be downloaded with detailed operation procedure at
https://github.com/ShusakuASANO/KYOCHAN_Chiral.
(14) Regueira, T.; Yan, W.; Stenby, E. H., Densities of the Binary
Systems n-Hexane plus n-Decane and n-Hexane plus n-Hexadecane
up to 60 MPa and 463 K. J. Chem. Eng. Data 2015, 60, 3631-3645.
(15) The enantiomeric excess values of the samples were determined by UV signal of PDA detector to avoid the influence of artifacts of CD detector.
(16) The range of Hrac‡ and Srac‡ are 26.9-27.8 kcal·mol–1 and
5.04-7.72 cal·mol–1·K–1, respectively, in consideration of the SE of
Eyring plot.
(17) 2a was newly synthesized in this study. See, the Supporting
Information for the detail of the synthesis.
(18) Garcia-Miaja, G.; Troncoso, J.; Romani, L., Density and Heat
Capacity as a Function of Temperature for Binary Mixtures of 1Butyl-3-methylpyridinium Tetrafluoroborate plus Water, plus Ethanol, and plus Nitromethane. J. Chem. Eng. Data 2007, 52, 22612265.
(19) The range of Hrac‡ and Srac‡ are 25.4-26.1 kcal·mol–1 and
2.49-4.39 cal·mol–1·K–1, respectively, in consideration of the SE of
Eyring plot.
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