Subscribe to RSS
DOI: 10.1055/s-2008-1067083
PMA-Silica Gel Catalyzed Propargylation of Aromatic Compounds with Arylpropargyl Alcohols under Solvent-Free Conditions [1]
Publication History
Publication Date:
16 May 2008 (online)

Abstract
PMA-silica gel has been utilized to catalyze efficiently the propargylation of aromatic compounds with arylpropargyl alcohols in the absence of solvent under environmentally benign conditions.
Key words
propargylation - nucleophilic substitution - Nicholas reaction - Friedel-Crafts alkylation
IICT Communication No. 061220
-
2a
Basavaiah D.Jaganmohan Rao A.Satyanarayana T. Chem. Rev. 2003, 103: 811 ; and references cited therein -
2b
Bandini M.Emer E.Tommasi S.Umani-Ronchi A. Eur. J. Org.Chem. 2006, 3527 -
2c
Kawamura M.Cui DM.Shimada S. Tetrahedron 2006, 62: 9201 -
2d
Chen X.Yu M.Wang M. J. Chem. Res. 2005, 80 -
2e
Cardoso LAM.Alves W.Gonzaga ARE.Aguiar LMG.Andrade HMC. J. Mol. Catal. A: Chem. 2004, 209: 189 -
2f
Sartori G.Maggi R. Chem. Rev. 2006, 106: 1077 -
3a
Nicholas KM.Mulvaney M.Bayer M. J. Am. Chem. Soc. 1980, 102: 2508 -
3b
Kuhn O.Rau D.Mayr H. J. Am. Chem. Soc. 1998, 120: 900 -
3c
Nicholas KM. Acc. Chem. Res. 1987, 20: 207 -
3d
Caffyn AJM.Nicholas KM. In Comprehensive Organometallic Chemistry II Vol. 12:Abel EW.Stone FGA.Wilkinson J. Pergamon Press; Oxford: 1995. Chap. 7.1. p.685 -
3e
Green JR. Curr. Org. Chem. 2001, 5: 809 - For various applications of Nicholas reactions see:
-
3f
Qunital MM.Colsser KD.Shea KV. Org. Lett. 2004, 6: 4949 -
3g
Berge J.Claridge S.Mann A.Muller C.Tyrrell E. Tetrahedron Lett. 1997, 38: 685 -
3h
Goering BK. Ph.D. Dissertation Cornell University; U.S.A.: 1995. -
3i
Montana AM.Fernandez D. Tetrahedron Lett. 1999, 40: 6499 -
4a
Sanz R.Martinez A.Alvarez-Gutierrez JM.Rodriguez F. Eur. J. Org. Chem. 2006, 1383 -
4b For other propargylations see:
Sanz R.Miguel D.Martinez A.Alvarez-Gutierrez JM.Rodriguez F. Org. Lett. 2007, 9: 727 -
4c
Karunakar GV.Periasamy M. J. Org. Chem. 2006, 71: 7463 - 5
Kennedy-Smith JJ.Young LA.Toste FD. Org. Lett. 2004, 6: 1325 -
6a
Nishibayashi Y.Yoshikawa M.Inada Y.Hidai M.Uemura S. Angew. Chem. Int. Ed. 2003, 42: 1495 -
6b
Nishibayashi Y.Yoshikawa M.Inada Y.Hidai M.Uemura S. J. Am. Chem. Soc. 2002, 124: 11846 -
6c
Fischmeister C.Toupet L.Dixneuf PH. New J. Chem. 2005, 29: 765 -
6d
Bustelo E.Dixneuf PH. Adv. Synth. Catal. 2007, 349: 933 -
6e For a review article see:
Nishibayashi Y.Uemura S. Curr. Org. Chem. 2006, 10: 135 - 7
Georgy M.Boucard V.Campagne J.-M. J. Am. Chem. Soc. 2005, 127: 14180 - 8
Liu JH.Muth E.Florke U.Henkel G.Merz K.Sauvageau J.Schwake E.Dyker G. Adv. Synth. Catal. 2006, 348: 456 - 9 For related reactions with bismuth see:
Qin H.Yamagiwa N.Matsunaga S.Shibasaki M. Angew. Chem. Int. Ed. 2007, 46: 409 -
10a
Zhan Z.-P.Yu J.-L.Liu H.-J.Cui Y.-Y.Yang R.-F.Yang W.-Z.Li J.-P. J. Org. Chem. 2006, 71: 8298 -
10b
Zhan Z.-P.Cui Y.-Y.Liu H.-J. Tetrahedron Lett. 2006, 47: 9143 -
11a
Anastas PT.Williamson TC. Green Chemistry, Designing for the EnvironmentAnastas PT.Williamson TC. American Chemical Society; Washington DC: 1996. p.1-17 -
11b
Anastas PT.Kirchhoff MM.Williamson TC. Appl. Catal., A 2001, 221: 3 - For our recent contributions see:
-
11c
Yadav JS.Subba Reddy BV. J. Mol. Catal. A: Chem. 2007, 274: 116 -
11d
Yadav JS.Reddy BVS.Lakshmi PN. J. Mol. Catal. A.: Chem. 2007, 274: 101 -
12a
Kozhevnikov IV. Chem. Rev. 1998, 98: 171 -
12b
Mizuno N.Misono M. Chem. Rev. 1998, 98: 199 -
12c
Misono M.Ono I.Koyano G.Aoshima A. Pure Appl. Chem. 2000, 72: 1305 -
12d
Wilson K.Clark JH. Pure Appl. Chem. 2000, 72: 1313 - 13
Crisostomo FRP.Carrillo R.Martin T.Martin VS. Tetrahedron Lett. 2005, 46: 2829 -
14a
Yadav JS.Satyanarayana M.Balanarsaiah E.Raghavendra S. Tetrahedron Lett. 2006, 47: 6095 -
14b
Yadav JS.Raghavendra S.Satyanarayana M.Balanarsaiah E. Synlett 2005, 2461 - For other applications of PMA-silica gel from other groups see:
-
14c
Kishore Kumar GD.Baskaran S. J. Org. Chem. 2005, 70: 4520 -
14d
Kishore Kumar GD.Baskaran S. Chem. Commun. 2004, 1026 -
14e
Kishore Kumar GD.Baskaran S. Synlett 2004, 1719 - 19 For the mechanism of transition-metal-stabilized propargyl cations, see:
Müller JJT. Eur. J. Org. Chem. 2001, 2021 - 20 For more details see:
Srihari P.Reddy JSS.Bhunia DC.Mandal SS.Yadav JS. Synth. Commun. 2008, 38: 1448
References
IICT Communication No. 061220
15Propargyl alcohols were prepared according to the earlier known procedures from monosubstituted acetylenes and corresponding aldehydes using EtMgBr.
16The compound 1a (Table [4] , entry 1) was studied for three runs (90%, 88%, and 85% yields respectively).
17All the reactions were run with 1 mol% PMA-silica gel at r.t. in MeCN unless specified.
18Substitution was present at the para position (least hindered site with high electron density) and was confirmed by 1H NMR spectroscopy. No other products were formed in this reaction.