3
12
13
K. C. Sproul, W. A. Chalifoux, Org. Lett., 2015, 17, 3334-3337.
Y. Yauchi, M. Ide, R. Shiogai, T. Chikugo, T. Iwasawa, Eur. J.
Org. Chem., 2015, 938-943.
M. Sridhar, J. Raveendra, M. K. K. Reddy, G. K. Reddy, V.V.
Sairam, Tetrahedron Lett. 2013, 54, 3993-3996.
a) R. N. Ram, V. K. Soni, D. K. Gupta, Tetrahedron, 2012, 68,
9068-9075. b) F. G. Menezes, H. Gallardo, C. Zucco, Quim. Nova
2010, 33, 2233-2244. c) H. Morimoto, S. H. Wiedemann, A.
Yamaguchi, S. Harada, Z. Chen, S. Matsunaga, M. Shibasaki,
Angew. Chem., Int. Ed. 2006, 45, 3146-3150. d) R. Silvestri, M.
Artico, G. La Regina, G. De Martino, M. La Colla, R. Loddo, P. La
Colla, IL Farmaco 2004, 59, 201-210. e) M. Uieara, C. Zucco, D.
Zanette, M. C. Rezende, F. Nome, J. Chem. Soc., Perkin Trans. 2,
1987,175-179.
To understand the reaction mechanism for formation of
1,2,2-triiodovinyl derivative in the present reaction, we
initially studied reaction of 1k with iodine and observed no
reaction. However, when 1k was treated with KOH and I2,
we observed formation of corresponding 1,2,2-triiodovinyl
derivative 4k. Here, reaction of KOH with I2 produces HOI.
Since alkynylsilanes are known to undergo halo desilylation
reaction with hypohalous acid to give 1-haloalkyne,11 it
appears that alkynylsilane initially reacts with HOI and
converts into 1-iodoalkyne which upon reaction with iodine
present in the reaction medium, transforms into 1,2,2-
triiodovinyl derivative. We believe that same mechanism is
operative also for the formation of 1,2,2-triiodovinyl
derivatives (4a-l) in the reaction of alkynylsilanes with oxone-
KI (eq.6, Scheme 2). Since HOX also can undergo further
transformation and convert into dihalo monoxide X2O (eq.
2),14 we believe that reaction of haloalkynes with X2O is
responsible for formation of α,α,α-trihalomethylketones (eq. 5,
Scheme 2). In this study, only electron rich alkynylsilanes
1a-h formed α,α,α-trihalomethylketones (2a-h and 3a-h) and
electron deficient alkynylsilanes 1i-l produced only 1,2,2-
trihalovinyl compounds (5i-l and 6i-l) under same reaction
conditions (eq. 6, Scheme 2).
14
15
16
17
a) C. A. Delcomyn, K. E. Bushway, M. V. Henley, Environ. Sci.
Technol, 2006, 40, 2759–2764. b) H. Hussain, I. R. Green, I.
Ahmed, Chem. Rev., 2013, 113, 3329−3371.
C. G. Swain, D. R. Crist, J. Am. Chem. Soc., 1972, 94, 3195–3200.
In conclusion, we showed simple and efficient methods
for preparation of trihalomethylketones and 1,2,2-trihalovinyl
derivatives from alkynylsilanes under mild conditions using
oxone as oxidant and KX (X=Cl, Br, I) as halogen source.
We also showed a simple one-pot method for efficient
transformation of an alkynylsilane into amides and esters.
Authors are thankful to CSIR, New Delhi for the
financial support under the project CSC-0123 (Indus Magic);
V.S., R.J. and S.K. are thankful to UGC, New Delhi for the
award of Junior Research Fellowship.
Supporting
Information
is
available
on
References and Notes
1
a) C. Mellin-Morliere, D. J. Aitken, S. D. Bull, S. G. Davies, H.
Husson, Tetrahedron: Asymmetry, 2001, 12, 149-155. b) H. Lebel,
H. Piras, J. Bartholomeus, Angew. Chem., Int. Ed., 2014, 53, 7300-
7304. c) H. Lebel, C. Spitz, O. Leogane, C. Trudel, M. Parmentier,
Org. Lett., 2011, 13, 5460–5463.
2
3
4
E. J. Corey, C. J. Helal, Tetrahedron Lett., 1993, 34, 5227-5230.
H. Wynberg, E. G. J. Staring, J. Org. Chem., 1985, 50, 1977-1979.
a) M. J. Kelly, US5675037, 1997. b) M. J. Kelly, A. M. Budenz,
US5767314, 1998.
5
a) R. N. Ram, V. K. Soni, D. K. Gupta, Tetrahedron, 2012, 68,
9068-9075. b) J. Houben, W. Fischer, Eur. J. Inorg. Chem., 1931,
64, 240-247.
6
J. Druzian, C. Zucco, M. C. Rezende, F. Nome, J. Org. Chem.,
1989, 54, 4767-4771.
7
I. A. Atanassova, J. S. Petrov, V. H. Ognjanova, N. M. Mollov,
Synth. Commun., 1990, 20, 2083-2090.
8
J. Houben, W. Fischer, Ber. Dtsch. Chem. Ges., B: Abhandlungen,
1931, 64B, 240-247.
9
M. Romero-Ortega, H. Reyes, A. Covarruvias-Zuniga, R. Cruz, J.
G. Avila-Zarraga, Synthesis, 2003, 18, 2765-2767.
a) A. A. Rexit, X. Hu, Tetrahedron, 2015, 71, 2313-2316. b) S.
Kamijo, S. Matsumura, M. Inoue, Tetrahedron Lett., 2012, 53,
4368-4371.
10
11
M. H. Vilhelmsen, A. S. Andersson, M. B. Nielsen, Synthesis, 2009,
9, 1469-1472.