D
R. G. Soengas et al.
Letter
Synlett
Taylor, R. T. Org. React. (N. Y.) 1991, 41, 91. (f) Miller, R. B.;
McGarvey, G. J. Org. Chem. 1978, 43, 4424. (g) Brown, H. C.;
Hamaoka, T.; Ravindran, N. J. Am. Chem. Soc. 1973, 95, 6456.
(3) Takai, K.; Nitta, K.; Utimoto, K. J. Am. Chem. Soc. 1986, 108, 7408.
(4) (a) Miura, K.; Ichinose, Y.; Nozaki, K.; Fugami, K.; Oshima, K.;
Utimoto, K. Bull. Chem. Soc. Jpn. 1989, 62, 143. (b) Abbas, S.;
Hayes, C. J.; Worden, S. Tetrahedron Lett. 2000, 41, 3215.
(5) (a) Uenishi, J.; Kawahama, R.; Yonemitsu, O. J. Org. Chem. 1998,
63, 8965. (b) Ranu, B. C.; Samanta, S.; Guchhait, S. K. J. Org.
Chem. 2001, 66, 4102.
Nitromethylations: (e) Soengas, R. G.; Silva, A. M. S. Synlett
2012, 23, 873. (f) Rodríguez-Solla, H.; Soengas, R. G.; Alvaredo,
N. Synlett 2012, 23, 2083.
(13) (a) Podlech, J.; Maier, T. C. Synthesis 2003, 633. (b) Ranu, B. C.;
Dutta, P.; Sarkar, A. J. Chem. Soc., Perkin Trans. 1 1999, 1139.
(c) Acúrcio, R.; Soengas, R. G.; Silva, A. M. S. Synlett 2014, 25,
1561.
(14) (a) Soengas, R. G.; Rodríguez-Solla, H.; Díaz-Pardo, A.; Acúrcio,
R.; Concellón, C.; del Amo, V.; Silva, A. M. S. Eur. J. Org. Chem.
2015, 2524. (b) Cho, S.; Kang, S.; Keum, G.; Kang, S. B.; Han, S.-
Y.; Kim, Y. J. Org. Chem. 2003, 68, 180.
(6) (a) Namy, J. L.; Girard, P.; Kagan, H. B. Nouv. J. Chem. 1977, 1, 5.
(b) Girard, P.; Namy, J. L.; Kagan, H. B. J. Am. Chem. Soc. 1980,
102, 2693.
(15) Soengas R. G., Silva V. L. M.: Pinto, J.; Rodríguez-Solla, H.; Silva,
A. M. S. Eur. J. Org. Chem. 2016, 99.
(7) Concellón, J. M.; Rodríguez-Solla, H. Chem. Soc. Rev. 2004, 33,
599.
(16) Concellón, J. M.; Rodríguez-Solla, H.; Bardales, E.; Huerta, M.
Eur. J. Org. Chem. 2003, 1775.
(8) Steel, P. G. J. Chem. Soc., Perkin Trans. 1 2001, 2727.
(9) Curran, D. P.; Fevig, T. L.; Jasperse, C. P.; Totleben, M. J. Synlett
1992, 943.
(10) Kunishima, M.; Hioki, K.; Ohara, T.; Tani, S. J. Chem. Soc., Chem.
Commun. 1992, 219.
(17) Samarium-Promoted Reduction of gem-Dibromoalkenes 1
(Method A); General Procedure
A 0.1 M solution of SmI2 in THF (0.8 mmol) was added to a
stirred solution of the appropriate gem-dibromoalkene 1 (0.4
mmol) in THF (5 mL). Deoxygenated H2O (0.5 mL) was added
and the mixture was stirred at r.t. for 3 h. The reaction was
quenched with 0.1 M aq HCl (10 mL) and the mixture was
extracted with CH2Cl2 (3 × 25 mL). The combined organic
extracts were washed with sat. aq Na2S2O3 (20 mL), dried
(MgSO4), filtered, and concentrated in vacuo.
(11) For reviews on indium chemistry, see: (a) Cintas, P. Synlett
1995, 1087. (b) Li, C. J. Tetrahedron 1996, 52, 5643. (c) Marshall,
J. A. Chemtracts: Org. Chem. 1997, 10, 481. (d) Li, C. J. In Green
Chemistry: Frontiers in Benign Chemical Syntheses and Processes;
Anastas, P.; Williamson, T. C., Eds.; Oxford University Press:
Oxford, 1998, Chap. 14. (e) Paquette, L. A. In Green Chemistry:
Frontiers in Benign Chemical Syntheses and Processes; Anastas,
P.; Williamson, T. C., Eds.; Oxford University Press: Oxford,
1998, Chap. 15. (f) Li, C. J.; Chan, T. K. Tetrahedron 1999, 55,
11149.
(12) Allylations: (a) Araki, S.; Kamei, T.; Hirashita, T.; Yamamura, H.;
Kawai, M. Org. Lett. 2000, 2, 847. (b) Tan, K.-T.; Chang, S.-S.;
Cheng, H.-S.; Loh, T.-P. J. Am. Chem. Soc. 2003, 125, 2958. Propar-
gylations: (c) Isaac, M. B.; Chan, T.-H. J. Chem. Soc., Chem.
Commun. 1995, 1003. Alkynylations: (d) Augé, J.; Lubin-Ger-
main, N.; Seghrouchni, L. Tetrahedron Lett. 2002, 43, 5255.
(18) Indium-Promoted Reduction of gem-Dibromoalkenes
1
(Method B); General Procedure
Indium metal (90 mg, 0.8 mmol), InCl3 (88 mg, 0.4 mmol), and
Pd(PPh3)4 (18 mg, 2 mol%) were added to a solution of the gem-
dibromoalkene 1 (0.4 mmol) in THF–H2O (1:1; 6 mL), and the
mixture was stirred at r.t. for 3 h. The reaction was quenched
with 1 M aq HCl (3 mL) and the mixture was diluted with H2O
(25 mL) and extracted with Et2O (3 × 25 mL). The organic
extracts were dried (Na2SO4), filtered, and concentrated under
reduced pressure.
(19) The physical data for compounds 2 were similar to those
reported in the corresponding literature; see refs. 2 and 3.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2016, 27, A–D