Organic Letters
Letter
In summary, we demonstrate an operationally simple and
time-efficient derivatization for chiral monoamines that leads to
observable ECCD signals. The derivatizing agent (1-BDN) can
be easily prepared in gram scale in high yield, and its reaction
with amines is facile and efficient. The CD signals arise from
exciton coupling of the bis-naphthyl rings, adopting a
preponderance of either the P or M helicity as a result of
minimizing interactions with the substituents at the asymmetric
center. The helicity, observed as either positive or negative
ECCD, is predicted easily through routine and expeditious
conformational search of all possible conformers. The
dominant population, calculated from a library of conformers
leading to either P or M helicity, provides an assignment of
absolute stereochemistry. The use of the bis-naphthyl moiety as
a sensor for absolute stereochemistry is not restricted to chiral
monoamines; use of the same concept for determining the
absolute stereochemistry of other families of molecules is
ongoing.
Welch, C. J. J. Org. Chem. 2016, 81, 1185. (s) Joyce, L. A.; Sherer, E.
C.; Welch, C. J. Chemical Science 2014, 5, 2855.
(3) (a) Berova, N., Polavarapu, P. L., Nakanishi, K., Woody, R. W.
Comprehensive Chiroptical Spectroscopy: Applications in Stereochemical
Analysis of Synthetic Compounds, Natural Products, and Biomolecules;
Wiley: Hoboken, 2012; Vol. 2. (b) Harada, N.; Nakanishi, K. Circular
Dichroic Spectroscopy: Exciton Coupling in Organic Stereochemistry;
University Science Books: Mill Valley, CA, 1983.
(4) (a) Yang, Q.; Olmsted, C.; Borhan, B. Org. Lett. 2002, 4, 3423.
(b) Proni, G.; Pescitelli, G.; Huang, X.; Quraishi, N. Q.; Nakanishi, K.;
Berova, N. Chem. Commun. 2002, 1590. (c) Tanasova, M.; Borhan, B.
Eur. J. Org. Chem. 2012, 2012, 3261. (d) Joyce, L. A.; Maynor, M. S.;
Dragna, J. M.; da Cruz, G. M.; Lynch, V. M.; Canary, J. W.; Anslyn, E.
V. J. Am. Chem. Soc. 2011, 133, 13746. (e) Huang, X.; Rickman, B. H.;
Borhan, B.; Berova, N.; Nakanishi, K. J. Am. Chem. Soc. 1998, 120,
6
185. (f) Li, X.; Burrell, C. E.; Staples, R. J.; Borhan, B. J. Am. Chem.
Soc. 2012, 134, 9026. (g) Anyika, M.; Gholami, H.; Ashtekar, K. D.;
Acho, R.; Borhan, B. J. Am. Chem. Soc. 2014, 136, 550. (h) Tanasova,
M.; Anyika, M.; Borhan, B. Angew. Chem., Int. Ed. 2015, 54, 4274.
(i) Gholami, H.; Anyika, M.; Zhang, J.; Vasileiou, C.; Borhan, B. Chem.
-
Eur. J. 2016, 22, 9235. (j) Aimi, J.; Oya, K.; Tsuda, A.; Aida, T. Angew.
ASSOCIATED CONTENT
Supporting Information
Chem., Int. Ed. 2007, 46, 2031. (k) Ikbal, S. A.; Dhamija, A.; Brahma,
S.; Rath, S. P. J. Org. Chem. 2016, 81, 5440. (l) Hayashi, S.; Yotsukura,
M.; Noji, M.; Takanami, T. Chem. Commun. 2015, 51, 11068.
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m) Hayashi, T.; Aya, T.; Nonoguchi, M.; Mizutani, T.; Hisaeda, Y.;
Kitagawa, S.; Ogoshi, H. Tetrahedron 2002, 58, 2803. (n) Ishii, Y.;
Onda, Y.; Kubo, Y. Tetrahedron Lett. 2006, 47, 8221. (o) Lintuluoto, J.
M.; Borovkov, V. V.; Inoue, Y. J. Am. Chem. Soc. 2002, 124, 13676.
Experimental details and spectroscopic data (PDF)
(
p) Redl, F. X.; Lutz, M.; Daub, J. Chem. - Eur. J. 2001, 7, 5350.
(
q) Zhang, J.; Holmes, A. E.; Sharma, A.; Brooks, N. R.; Rarig, R. S.;
AUTHOR INFORMATION
Zubieta, J.; Canary, J. W. Chirality 2003, 15, 180.
5) (a) Dale, J. A.; Mosher, H. S. J. Am. Chem. Soc. 1973, 95, 512.
b) Fukui, H.; Fukushi, Y. Org. Lett. 2010, 12, 2856. (c) Hoye, T. R.;
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(
Erickson, S. E.; Erickson-Birkedahl, S. L.; Hale, C. R. H.; Izgu, E. C.;
ORCID
Mayer, M. J.; Notz, P. K.; Renner, M. K. Org. Lett. 2010, 12, 1768.
(d) Porto, S.; Quinoa, E.; Riguera, R. Tetrahedron 2014, 70, 3276.
(e) Takeuchi, Y.; Segawa, M.; Fujisawa, H.; Omata, K.; Lodwig, S. N.;
Unkefer, C. J. Angew. Chem., Int. Ed. 2006, 45, 4617.
Notes
(6) (a) Wenzel, T. J.; Wilcox, J. D. Chirality 2003, 15, 256. (b) Seco,
J. M.; Quinoa,
7) (a) You, L.; Berman, J. S.; Anslyn, E. V. Nat. Chem. 2011, 3, 943.
b) Jo, H. H.; Edupuganti, R.; You, L.; Dalby, K. N.; Anslyn, E. V.
́
E.; Riguera, R. Chem. Rev. 2004, 104, 17.
The authors declare no competing financial interest.
(
(
ACKNOWLEDGMENTS
We are grateful to the NSF (CHE-1213759) for funding.
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Chem. Sci. 2015, 6, 158.
(8) (a) Superchi, S.; Bisaccia, R.; Casarini, D.; Laurita, A.; Rosini, C. J.
Am. Chem. Soc. 2006, 128, 6893. (b) Mazaleyrat, J. P.; Wright, K.;
Gaucher, A.; Toulemonde, N.; Wakselman, M.; Oancea, S.; Peggion,
C.; Formaggio, F.; Setnicka, V.; Keiderling, T. A.; Toniolo, C. J. Am.
Chem. Soc. 2004, 126, 12874. (c) Dutot, L.; Wright, K.; Gaucher, A.;
Wakselman, M.; Mazaleyrat, J. P.; De Zotti, M.; Peggion, C.;
Formaggio, F.; Toniolo, C. J. Am. Chem. Soc. 2008, 130, 5986.
REFERENCES
1) Lu, H.; Kobayashi, N. Chem. Rev. 2016, 116, 6184.
2) (a) Bentley, K. W.; Zhang, P.; Wolf, C. Sci. Adv. 2016, 2,
■
(
(
No. e1501162. (b) Mei, X.; Wolf, C. J. Am. Chem. Soc. 2004, 126,
4736. (c) Zahn, S.; Canary, J. W. Science 2000, 288, 1404.
d) Yashima, E.; Nimura, T.; Matsushima, T.; Okamoto, Y. J. Am.
1
(
(
d) Tartaglia, S.; Pace, F.; Scafato, P.; Rosini, C. Org. Lett. 2008, 10,
3
421.
Chem. Soc. 1996, 118, 9800. (e) Kuwahara, S.; Nakamura, M.;
Yamaguchi, A.; Ikeda, M.; Habata, Y. Org. Lett. 2013, 15, 5738.
(9) Hosoi, S.; Kamiya, M.; Ohta, T. Org. Lett. 2001, 3, 3659.
(10) The prediction of helicity for naphthyl-containing substrates is
(
f) Zhang, P.; Wolf, C. Chem. Commun. 2013, 49, 7010. (g) Seo, M. S.;
complicated due to the contribution of the aromatic group in the
overall ECCD of the BDN-derivatized sample. The pairwise coupling
of three naphthyl groups (one from the substrate and two from BDN)
Lee, A.; Kim, H. Org. Lett. 2014, 16, 2950. (h) You, L.; Zha, D.;
Anslyn, E. V. Chem. Rev. 2015, 115, 7840. (i) AkritopoulouZanze, I.;
Nakanishi, K.; Stepowska, H.; Grzeszczyk, B.; Zamojski, A.; Berova, N.
Chirality 1997, 9, 699. (j) Berova, N.; Pescitelli, G.; Petrovic, A. G.;
Proni, G. Chem. Commun. 2009, 5958. (k) Degenbeck, H.; Felten, A.
S.; Escudero-Adan, E. C.; Benet-Buchholz, J.; Di Bari, L.; Pescitelli, G.;
Vidal-Ferran, A. Inorg. Chem. 2012, 51, 8643. (l) Eelkema, R.; Feringa,
B. L. J. Am. Chem. Soc. 2005, 127, 13480. (m) Goto, H.; Furusho, Y.;
Yashima, E. Chem. Commun. 2009, 1650. (n) Wezenberg, S. J.; Salassa,
G.; Escudero-Adan, E. C.; Benet-Buchholz, J.; Kleij, A. W. Angew.
Chem., Int. Ed. 2011, 50, 713. (o) Wolf, C.; Bentley, K. W. Chem. Soc.
Rev. 2013, 42, 5408. (p) Zhao, Y. C.; Swager, T. M. J. Am. Chem. Soc.
(
(
(
11) Winstein, S.; Holness, N. J. J. Am. Chem. Soc. 1955, 77, 5562.
12) Charton, M. J. Am. Chem. Soc. 1975, 97, 1552.
13) Verloop, A.; Tipker, J. In Biological Activity and Chemical
Structure; Elsevier, 1977.
14) Zhou, Y. T.; Ren, Y. L.; Zhang, L.; You, L.; Yuan, Y. F.; Anslyn,
E. V. Tetrahedron 2015, 71, 3515.
(
2
015, 137, 3221. (q) Yang, L.; Wenzel, T.; Williamson, R. T.;
Christensen, M.; Schafer, W.; Welch, C. J. ACS Cent. Sci. 2016, 2, 332.
r) Bentley, K. W.; Joyce, L. A.; Sherer, E. C.; Sheng, H.; Wolf, C.;
(
D
Org. Lett. XXXX, XXX, XXX−XXX