4
Tetrahedron Letters
cyclopropanation of similar type intermediate is well-known,16 our
5. (a) Sakemi, S.; Higa, T.; Jefford, C.W.; Bernardinelli, G. Tetrahedron Lett.
1986, 27, 4287-4290. (b) Qin, J.; Su, H.; Zhang, Y.; Gao, J.; Zhu, L.; Wu, X.;
Pan, H.; Li, X. Bioorg. Med. Chem. Lett. 2010, 20, 7152.
approach can be utilized for a concise route to the (±)-cyclolaurene
(2a) (Figure 1).
6. Ayyad, S. -E. N. Al-Footy, Kh. O.; Alarif, W. M.; Sobahi, T. R.; Basaif, S.
A.; Makki, M. S.; Asiri, A. M.; Al Halwani, A.Y.; Badria, F. A. Chem.
Pharm. Bull. 2011, 59, 1294.
Me
O
Me
Et3N, MsCl
CH2Cl2, 0 °C
HO
Me
MeLi, THF
0 °C, 2 h
Me
Me
Me
Me
91%
89%
7. (a) Kumar, R.; Halder, J.; Nanda, S. Tetrahedron: Asymmetry 2017, 73,
809. (b) Srikrishma, A.; Satanarayana, G.; Prasad, K. R. Synth. Commun.
2007, 37, 1511. (c) Graninger, R. S.; Patel, A. Chem. Commun. 2003, 1072.
(d) Nayek, A.; Drew, M. G. B.; Ghosh, S. Tetrahedron 2003, 59, 5175. (e)
Aavual, B. R.; Cui, Q.; Mash, A. Tetrahedron: Asymmetry 2000, 11, 4681
and references cited.
Me
17
mixture of
diastereomers
(
)
11
(
)
(±)-isolaurene
1a
Me
Me
Me
[(±)-
]
Scheme 6. Total synthesis of (±)-isolaurene (1a).
8. (a) Enzell, C.; Erdtman, H. Tetrahedron 1958, 4, 361. (b) Erdtman, H.;
Thomas, B. R. Acta Chem Scand. 1958, 12, 267. (c) Chetty, G. L.; Dev, S.
Tetrahedron Lett. 1964, 5, 73.
Later, following our proposed strategy, MeLi addition onto 2-
methyl 3-(p-tolyl)-cyclopenten-2-ones 11 furnished tertiary alcohol
17 in the form of mixture of diastereomers (Scheme 6). A similar
dehydration/elimination of tertiary alcohol 17 as shown in Scheme 5
was carried out under mesylation condition to complete the total
synthesis of (±)-isolaurene (1a) in 89% yield.
9. (a) Matsuo, A.; Yuki, S.; Nakayama, M.; Hayashi, S. J. Chem. Soc., Chem.
Commun. 1981, 16, 864. (b) Fraga, B. M. Nat. Prod. Rep. 2006, 23, 943. (c)
Ichiba, T.; Higa, T. J. Org. Chem. 1986, 51, 3364. (d) Shizuri, Y.; Yamada,
A.; Yamada, K. Phytochemistry 1984, 23, 2672. (e) For a review, see;
Bideau, F. L.; Kousara, M.; Chen, L.; Wei, L.; Dumas, F. Chem. Rev. 2017,
117, 6110.
To conclude, a concise total synthesis of (±)-isolaurene (1a) has
been achieved in 5 steps (58.3% overall yields) starting from 2-
10. Our report on the synthesis of (±)-laurokamurene B, see; Das, M. K.;
methyl cyclopentane 1,3-dione following
a
Stork-Danheiser
Dinda,
B.;
Bisai,
V.
Tetrahedron
Lett.
2019,
sequence and a Ni(II)-catalyzed conjugate addition as key synthetic
transformations. It is believed that a catalytic enantioselective
version of this strategy can be envisioned if the advanced
intermediate 2-methyl 3-(p-tolyl)-3-methyl cyclopentanone (11) is
synthesized in enantioenriched form.17 Further investigation towards
this direction as well as application of this strategy for the synthesis
of complex dimeric cyclolaurenes (such as 3) is currently under
active investigation.
11. Selected reports on the synthesis of (±)-cuparene, see: (b) Secci, F.;
Frongia, A.; Ollivier, J.; Piras, P. P. Synthesis 2007, 7, 999. (c) Cohen, T.;
Kreethadumrongdat, T.; Liu, X.; Kulkarni, V. J. Am. Chem. Soc. 2001, 123,
3478. (d) Bailey, W. F.; Khanolkar, A. D. Tetrahedron 1991, 47, 7727. (e)
Krief, A.; Barbeau, P. Synlett 1990, 511. Asymmetric total syntheses of
cuparenes, see: (f) Fuganti, C.; Serra, S. J. Org. Chem. 1999, 64, 8728. (g)
Ichiba, T.; Higa, T. J. Org. Chem. 1986, 51, 3364.
12. Selected reports on the synthesis of (±)-herbertene, see: (a) Bernard, A.
M.; Frongia, A.; Secci, F.; Piras, P. P. Chem. Commun. 2005, 3853. (b)
Gupta, P. D.; Pal, A.; Roy; Mukherjee, D. Tetrahedron Lett. 2000, 41, 7563.
(c) Ho, T.-L. J. Chem. Soc., Perkin. Trans. 1 1999, 2479. (d) Mandelt, K.;
Fitjer, L. Synthesis 1998, 1523. Asymmetric total syntheses of herbertenes,
see: (e) Nayek, A.; Ghosh, S. Tetrahedron Lett. 2002, 43, 1313. (f) Abad, A.;
Agullo, C.; Cunat, A. C.; Perni, R. H. J. Org. Chem. 1999, 64, 1741. (g) Tori,
M.; Miyako, T.; Sono, M. Tetrahedron: Asymmetry 1997, 8, 2731. (h)
Takano, S.; Moriya, M.; Ogassawara, K. Tetrahedron Lett. 1992, 33, 329.
Acknowledgments
V.B. thanks the Science and Engineering Research Board (SERB),
Department of Science and Technology (DST) for a research grant
[CS-021/2014]. Facilities from Department of Chemistry, IISER
Bhopal is gratefully acknowledged.
Supplementary data
13. (a) Fadel, A.; Canet, J.-L.; Salaün, J. Tetrahedron: Asymmetry 1993, 4,
27. (b) Tonari, K.; Ichimoto, I.; Ueda, H. Agric. Biol. Chem. 1980, 44, 625.
(c) Tomari, K.; Machiya, K.; Ichimoto, I.; Ueda, H. Agric. Biol. Chem. 1980,
44, 2135. (d) McMurry, J. E.; von Beroldingen, L. A. Tetrahedron 1974, 30,
2027. (e) Taber, D. F.; Anthony, J. M. Tetrahedron Lett. 1980, 21, 2779. (f)
Schuda, P. F.; Potlock, S. J.; Ziffer, H. Tetrahedron 1987, 43, 463. (g)
Srikrishna, A.; Sunderbabu, G. Tetrahedron Lett. 1989, 30, 3561. (h)
Srikrishna, A.; Sundarababu, G. Tetrahedron 1990, 46, 3601. (i) Srikrishna,
A.; Sundarababu, G. Tetrahedron 1991, 47, 481.
Supplementary data associated with this article can be found, in
the online version, at http:.....................
§Current Address:
The AB Research Group, Department of Chemistry, Indian Institute
of Science Education and Research Bhopal, Bhopal Bypass Road,
Bhopal - 462 066, India.
14. We have adopted a Ni(II)-catalyzed conjugate addition of methyl group
used by Cossy, for referenece, see; Cossy, J.; Gille, B.; BouzBouz, S.;
Belostta, V. Tetrahedron Lett. 1997, 38, 4069.
References and notes:
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16. For cyclopropanation of similar cyclopentenes, see; Kita, Y.;
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