Page 3 of 3
Journal Name
ChemComm
DOI: 10.1039/C4CC08562K
‡ These authors contributed equally.
1. K. C. Nicolaou and E. J. Sorensen, Classics in Total Synthesis; VCH:
New York, 1996.
2.
3.
K. C. Nicolaou and S. A. Snyder, Classics in Total Synthesis II;
Wiley-VCH: Weinheim, 2003.
K. C. Nicolaou and J. S. Chen, Classics in Total Synthesis III; Wiley-
VCH: New York, 2011.
4. T. Gaich and P. S. Baran, J. Org. Chem., 2010, 75, 4657.
5. I. Muhammad, X. C. Li, M. R. Jacob, B. L. Tekwani, D. C. Dunbar
and D. Ferreira, J. Nat. Prod., 2003, 66, 804.
6. Y. Gaoni and R. Mechoulam, J. Am. Chem. Soc., 1964, 86, 1646.
7. E. C. Taylor, K. Lenard and Y. Shvo, J. Am. Chem. Soc., 1966, 88
,
367.
8. L. Garrido, E. Zubı´a, M. J. Ortega and J. Salva, J. Nat. Prod., 2002,
65, 1328.
Scheme 4. Synthesis of analogues of tetrahydrocannabinols
Independent coupling of alcohol 14 and ent 14 with olivetol
9. M. Toyota, T. Shimamura, H. Ishii, M. Renner, J. Braggins and Y.
Asakawa, Chem. Pharm. Bull., 2002, 50, 1390.
-
furnished both the enantiomers of ∆8- and ∆9-THC.
Furthermore, this reaction was robust and was conducted on a
gram-scale synthesis of ∆9-THC yielding 1.12 g of it. Coupling
of alcohol 14 with various resorcinol derivatives generated half
a dozen congeners of tetrahydrocannabinols 23-29. Although
till date many syntheses of ∆9- THC are reported in literature, to
10. K. Minagawa, S. Kouzuki, K. Nomura, Y. Kawamura, H. Tani, Y.
Terui, H. Nakai and T. J. Kamigauchi, Antibiot., 2001, 54, 896.
11. (a) W.E. Childers and H. W. Pinnick, J. Org. Chem., 1984, 49, 5276;
(b) L. Crombie, W. M. L. Crombie, S. V. Jamieson and C. J. Palmer,
J. Chem. Soc. Perkin Trans.1, 1988, 1243; (c) D. A. Evans, E. A.
Shaughnessy and D. M. Barnes, Tetrahedron Lett., 1997, 38, 3193;
(d) L. Crombie, W. M. L. Crombie, C. J. Palmer and S. V. Jamieson,
Tetrahedron Lett., 1983, 24, 3129; (e) R. W. Rickards and H.
Ronnen-berg, J. Org. Chem., 1984, 49, 572; (f) S. H. Baek, M.
Srebnik and R. Mechoulam, Tetrahedron Lett., 1985, 26, 1083; (g) V.
Vaillancourt and K. F. Albizati, J. Org. Chem., 1992, 57, 3627; (h) A.
best of our knowledge, only one synthesis each of ∆8-THC 9 16
conicol 10
17 perrottetinene 1118 and epi-perrottetinene 2318 are
,
,
reported in literature.
Conclusions
D. William and Y. Kobayashi, Org. Lett., 2001, 3, 2017; (i) A. D.
Using a simple strategy we have achieved enantiospecific total
syntheses of structurally diverse natural products isolated from
different sources and having wide range of biological activities.
Synthesis of both natural products and their enantiomers has
been achieved in highly atom economical, protecting group free
William and Y. Kobayashi, J. Org. Chem., 2002, 67, 8771; (j) L. E;
Pearson, N. Kanizaj, A. C. Willis, M. N. Paddon-Row and M. S.
Sherburn, Chem. Eur. J., 2010, 16, 8280; (k) E. Ballerini, L. Minuti
and O. Piermatti, J. Org. Chem., 2010, 75, 4251; (l) Q. Huang, B.
Ma, X. Li, X. Pan and X. She, Synthesis., 2010, 11, 1766; (m) L.
Minuti and E. Ballerini, J. Org. Chem., 2011, 76, 5392; (n) D. A.
Evans, E. A. Shaughnessy and D. M. Barnes, Tetrahedron Lett.,
1997, 38, 3193; (o) D. A. Evans, D. M. Barnes, J. S. Johnson, T.
Lectka, P. V. Matt, S. J. Miller, J. A. Murry, R. D. Norcross, E. A.
Shaughnessy and K. R. Campos, J. Am. Chem. Soc., 1999, 121, 7582;
and in less than 6 steps longest linear sequence starting from
R-
(+) and S-(-)-limonene. Finally it is worth mentioning that with
a good strategy, even the Friedel-Crafts reaction can help solve
total synthesis problems that have either not yet been solved or
have required many steps through other routes.
We thank Prof. Viresh H. Rawal, University of Chicago, for
his suggestions and comments to improve the manuscript
substantially. We thank Mr. Dipankar Sahoo and Prosenjit Daw
for crystal structures. R. D. E., S. D. and V. K. thank CSIR,
New Delhi, and S. M. thanks UGC, New Delhi, for the award
of research fellowship. Financial support from IIT Kanpur and
DST, New Delhi (SB/S1/OC-01/2014) is gratefully
acknowledged.
(p) B. M. Trost and K. Dogra, Org. Lett., 2007, 9, 861.
12. Q. Wang, Q. Huang, B. Chen, J. Lu, H. Wang, X. She and X. Pan,
Angew. Chem. Int. Ed., 2006, 45, 3651.
13. A. Srikrishna and D. H. Dethe, Tetrahedron Lett., 2003, 44, 7817.
14. Z. L. Song, C. A. Fan and Y. Q. Tu, Chem. Rev., 2011, 111, 7523.
15. CCDC 1017678 (+)-22 contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The
Cambridge
Crystallographic
Data
Centre
via
Notes and references
aDepartment of Chemistry, Indian Institute of Technology Kanpur,
16. L. J. Cheng, J. H. Xie, Y. Chen, L. X. Wang and Q. L. Zhou, Org.
Lett., 2013, 15, 764.
2597436; Tel: + 91-512-2596537
+ 91-512-
17. B. C. Hong, P. Kotame, C. W. Tsai and J. H. Liao, Org. Lett., 2010,
12, 776.
†
Electronic supplementary information (ESI) available. CCDC
18. Y. Song, S. Hwang, P. Gong, D. Kim and S. Kim, Org. Lett., 2008,
10, 269.
1017678 (+22). For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/c000000x/
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3