3509
J. E. M. Fernando et al.
Paper
Synthesis
1,2,3,4-Tetrahydronaphthalen-2-yl Formate (5s)
A. J. Org. Chem. 2002, 67, 5152. For other in situ activation strat-
egies see ref. 1b and: (c) Olah, G. A.; Vankar, Y. D.; Arvanaghi,
M.; Sommer, J. Angew. Chem., Int. Ed. Engl. 1979, 18, 614.
(6) For the use of formyl Bt 2: (a) Katritzky, A. R.; Chang, H.-X.;
Yang, B. Synthesis 1995, 503. For a recent synthesis of this
reagent see: (b) Pasqua, A. E.; Matheson, M.; Sewell, A. L.;
Marquez, R. Org. Process Res. Dev. 2011, 15, 467. For use of
formate 3 see: (c) Hill, D. R.; Hsiao, C.-N.; Kurukulasuriya, R.;
Wittenberger, S. J. Org. Lett. 2002, 4, 111.
(7) For representative acid catalyzed approaches see: (a) Nakatake,
D.; Yokote, Y.; Matsushima, Y.; Yazakia, R.; Ohshima, T. Green
Chem. 2016, 18, 1524. (b) Iranpoor, N.; Firouzabadi, H.; Zolfigol,
M. A. Synth. Commun. 1998, 28, 1923. (c) Nishiguchi, T.;
Kawamine, K.; Ohtsuka, T. J. Org. Chem. 1992, 57, 312.
Yield: 141 mg (80%). 1H and 13C NMR data were identical with the lit-
erature.19
1,2,3,4-Tetrahydronaphthalen-1-yl Formate (5t)
Yield: 152 mg (86%). 1H and 13C NMR data were identical with the lit-
erature.6a
(–)-Menthyl Formate (5u)
Yield: 171 mg (93%). 1H and 13C NMR data were identical with the lit-
erature.20
Dihydrocholesterol-Derived Formate 5v
(8) For
a selection of recent reviews on NHC catalysis see:
White solid; yield: 313 mg (75%); Rf = 0.7 (EtOAc/PE, 1:9).
(a) Enders, D.; Niemeier, O.; Henseler, A. Chem. Rev. 2007, 107,
5606. For homoenolate chemistry see: (b) Nair, V.; Menon, R. S.;
Biju, A. T.; Sinu, C. R.; Paul, R. R.; Jose, A.; Sreekumar, V. Chem.
Soc. Rev. 2011, 40, 5336. (c) Douglas, J.; Churchill, G.; Smith, A.
D. Synthesis 2012, 44, 2295. For cascade catalysis see:
(d) Grossmann, A.; Enders, D. Angew. Chem. Int. Ed. 2012, 51,
314. For acyl anion chemistry see: (e) Bugaut, X.; Glorius, F.
Chem. Soc. Rev. 2012, 41, 3511. For applications in total synthe-
sis see: (f) Izquierdo, J.; Hutson, G. E.; Cohen, D. T.; Scheidt, K. A.
Angew. Chem. Int. Ed. 2012, 51, 11686. For acyl anion free cataly-
sis see: (g) Ryan, S. J.; Candish, L.; Lupton, D. W. Chem. Soc. Rev.
2013, 42, 4906. For catalysis under oxidative conditions see:
(h) De Sarkar, S.; Biswap, A.; Samanta, R. C.; Studer, A. Chem.
Eur. J. 2013, 19, 4664. For acyl azoliums and enol azoliums see:
(i) Mahatthananchai, J.; Bode, J. W. Acc. Chem. Res. 2014, 47, 696.
(j) Zhang, C.; Hooper, J. F.; Lupton, D. W. ACS Catal. 2017, 7,
2583. For an introduction to NHCs see: (k) Hopkinson, M. N.;
Richter, C.; Schedler, M.; Glorius, F. Nature (London) 2014, 510,
485. (l) Flanigan, D. M.; Romanov-Michailidis, F.; White, N. A.;
Rovis, T. Chem. Rev. 2015, 115, 9307.
IR (ATR): 2932s, 2849s, 1727s, 1466m, 1445m, 1373w, 1177s, 1131m,
995w, 922m, 867w, 803w cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.02 (s, 1 H), 4.86–4.77 (m, 1 H), 1.99–
1.94 (m, 1 H), 1.87–0.95 (m, 30 H), 0.90–0.85 (m, 9 H), 0.82 (s, 3 H),
0.65 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 160.9, 73.9, 56.6, 56.42, 56.36, 44.8,
44.7, 40.1, 39.7, 36.9, 36.3, 36.0, 35.61, 35.59, 34.1, 32.1, 28.7, 28.4,
28.2, 27.6, 24.4, 24.0, 23.0, 22.7, 21.4, 18.8, 12.4, 12.2.
MS (EI): m/z [M]+ calcd for C28H48O2: 416.4; found: 416.3.
Adamantan-1-yl Formate (5w)
Yield: 108 mg (60%). 1H and 13C NMR data were identical with the lit-
erature.20
Acknowledgment
D.W.L. thanks the ARC for financial support through the Future Fel-
lowship and Discovery programs.
(9) For selected examples: (a) Ryan, S. J.; Candish, L.; Lupton, D. W.
J. Am. Chem. Soc. 2009, 131, 14176. (b) Candish, L.; Lupton, D. W.
Org. Lett. 2010, 12, 4836. (c) Candish, L.; Lupton, D. W. Org.
Biomol. Chem. 2011, 9, 8182. (d) Candish, L.; Levens, A.; Lupton,
D. W. J. Am. Chem. Soc. 2014, 136, 14397. (e) Levens, A.; Zhang,
C.; Candish, L.; Forsyth, C. M.; Lupton, D. W. Org. Lett. 2015, 17,
5332.
(10) For a highlight on ester oxidation state NHC catalysis see:
Chauhan, P.; Enders, D. Angew. Chem. Int. Ed. 2014, 53, 1485.
(11) For seminal contributions see: (a) Grasa, G. A.; Kissling, R. M.;
Nolan, S. P. Org. Lett. 2002, 4, 3583. (b) Nyce, G. W.; Lamboy, J.
A.; Connor, E. F.; Waymouth, R. M.; Hedrick, J. L. Org. Lett. 2002,
4, 3587. (c) Suzuki, Y.; Yamauchi, K.; Muramatsu, K.; Sato, M.
Chem. Commun. 2004, 2770. (d) Kano, T.; Sasaki, K.; Maruoka, K.
Org. Lett. 2005, 7, 1347.
(12) Jereb, M.; Vražič, D.; Zupan, M. Tetrahedron Lett. 2009, 50, 2347.
(13) (a) Enders, D.; Breuer, K.; Teles, J. H. Helv. Chim. Acta 1996, 79,
1217. For the properties and stoichiometric reactions of this
carbene see: (b) Enders, D.; Breuer, K.; Raabe, G.; Runsink, J.;
Teles, J. H.; Melder, J.-P.; Ebel, K.; Brode, S. Angew. Chem., Int. Ed.
Engl. 1995, 34, 1021.
(14) Studies implicating Brønsted base pathways in transesterifica-
tion reactions see: (a) Movassaghi, M.; Schmidt, M. A. Org. Lett.
2005, 7, 2453. (b) Lai, C.-L.; Lee, H. M.; Hu, C.-H. Tetrahedron
Lett. 2005, 46, 6265.
Supporting Information
Supporting information for this article is available online at
procedures, characterization of all new compounds and copies of 1H
and 13C NMR spectra.
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References
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, 3505–3510