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DOI: 10.1055/s-2006-944222
Carbonyl Propargylation and Allenylation with 2-Propynyl Mesylates, Tin(IV) Iodide, and Tetrabutylammonium Iodide Controlled by Either a Steric Effect or Coordination Effect
Publication History
Publication Date:
04 July 2006 (online)
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Abstract
A combination of tin(IV) iodide and tetrabutylammonium iodide can be used for propargylation or allenylation of aldehydes with 2-propynyl mesylates in dichloromethane. 1-Methyl-2-propynyl mesylate or 2-butynyl mesylate results in propargylation or allenylation controlled by the steric effect of the 1- or 3-methyl group, and 3-trimethylsilyl-2-propynyl mesylate results in propargylation controlled by the coordination of triiodostannate to silane.
Key words
nucleophilic addition - propargylation - allenylation - tin(IV) iodide - tetrabutylammonium iodide
-
1a
Klein J. In The Chemistry of the Carbon-Carbon Triple BondPatai S. Wiley; New York: 1978. p.343 -
1b
Moreau J.-L. In The Chemistry of Ketenes, Allenes, and Related CompoundsPatai S. Wiley; New York: 1980. p.363 -
1c
Schuster HF.Coppola GM. Allenes in Organic Synthesis Wiley; New York: 1984. -
1d
Yamamoto H. In Comprehensive Organic Synthesis Vol. 2:Trost MB.Fleming I. Pergamon; Oxford: 1991. p.81 -
1e
Modern Acetylene Chemistry
Stang PJ.Diederich F. VCH; Weinheim: 1995. -
2a
Mukaiyama T.Harada T. Chem. Lett. 1981, 621 -
2b
Boldrini GP.Tagliavini E.Trombini C.Umani-Ronchi A. J. Chem. Soc., Chem. Commun. 1986, 685 -
2c
Tanaka H.Hamatani T.Yamashita S.Torii S. Chem. Lett. 1986, 1461 -
2d
Iyoda M.Kanao Y.Nishizaki M.Oda M. Bull. Chem. Soc. Jpn. 1989, 62: 3380 -
2e
Belyk K.Rozema MJ.Knochel P. J. Org. Chem. 1992, 57: 4074 -
2f
Yavari I.Riazi-Kermani F. Synth. Commun. 1995, 25: 2938 -
2g
Houllemare D.Outurquin F.Paulmier C. J. Chem. Soc., Perkin Trans. 1 1997, 1629 -
2h
Bieber LW.da Silva MF.da Costa RC.Silva LOS. Tetrahedron Lett. 1998, 39: 3655 -
2i
Kundu A.Prabhakar S.Vairamani M.Roy S. Organometallics 1999, 18: 2782 -
2j
Banerjee M.Roy S. Chem. Commun. 2003, 534 -
2k
Banerjee M.Roy S. Org. Lett. 2004, 6: 2137 - For representative non-Barbier-type selective carbonyl allenylations and propargylations, see:
-
3a
Nokami J.Tamaoka T.Koguchi T.Okawara R. Chem. Lett. 1984, 1939 -
3b
Suzuki M.Morita Y.Noyori R. J. Org. Chem. 1990, 55: 441 -
3c
Brown HC.Khire UR.Narla G.Racherla US. J. Org. Chem. 1995, 60: 544 -
3d
Kobayashi S.Nishio K. J. Am. Chem. Soc. 1995, 117: 6392 -
3e
Marshall JA.Yu RH.Perkins JF. J. Org. Chem. 1995, 60: 5550 -
3f
Marshall JA.Grant CM. J. Org. Chem. 1999, 64: 8214 -
3g
Nakajima M.Saito M.Hashimoto S. Tetrahedron: Asymmetry 2002, 13: 2449 ; and references cited therein - For the preparation of allenyltin and propargyltin compounds, see:
-
4a
Guillemin J.-C.Malagu K. Organometallics 1999, 18: 5259 -
4b
Kjellgren J.Sunden H.Szabo KJ. J. Am. Chem. Soc. 2005, 127: 1787 - 5
Lin MJ.Loh TP. J. Am. Chem. Soc. 2003, 125: 13042 - 6
Masuyama Y.Watabe A.Kurusu Y. Synlett 2003, 1713 -
7a
Masuyama Y.Ito A.Fukuzawa M.Terada K.Kurusu Y. Chem. Commun. 1998, 2025 -
7b
Masuyama Y.Watabe A.Ito A.Kurusu Y. Chem. Commun. 2000, 2009 - 8 For carbonyl allylation with SnI4 and TBAI, see:
Masuyama Y.Takeuchi K.Kurusu Y. Tetrahedron Lett. 2005, 46: 2861 -
10a Since 1b caused no carbonyl propargylation, 3-methylpropargyltriiodotin would scarcely isomerize to 1-methylallenyltriiodotin on account of the steric hindrance of the methyl group. Thus, the bulkier trimethylsilyl group should give an unusual effect for the isomerization of A to C. It is presumed that the formation of a higher coordinated silicon intermediate causes regioselective ring-opening reactions of α-silylepoxides at the α-carbon near to the silyl group:
Eisch JJ.Galle JE. J. Org. Chem. 1976, 41: 2615 -
10b
Soderquist JA.Santiago B. Tetrahedron Lett. 1989, 30: 5693 . Following the ring-opening reactions of α-silyl-epoxides, we propose stannylsilicate B as a plausible intermediate for the isomerization of A to C
References and Notes
It was confirmed by 1H NMR analysis (JEOL Λ-500) that the reaction of 4 (0.03 mmol) with SnI2 (0.04 mmol) and NaI (0.04 mmol) in DMF-d 7 (0.5 mL) at 25 °C first produced propargyltin A, δ = 4.06 ppm (CH2, s), and then produced a small yield of allenyltin C, δ = 4.90 ppm (C = CH2, s).