Carbonyl Propargylation and Allenylation with 2-Propynyl Mesylates, Tin(IV) Iodide, and Tetrabutylammonium Iodide Controlled by Either a Steric Effect or Coordination Effect

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.

nucleophilic addition - propargylation - allenylation - tin(IV) iodide - tetrabutylammonium iodide

References and Notes

<A NAME="RU03006ST-1A">1a</A> Klein J. In The Chemistry of the Carbon-Carbon Triple Bond   Patai S. Wiley; New York: 1978.  p.343 

<A NAME="RU03006ST-1B">1b</A> Moreau J.-L. In The Chemistry of Ketenes, Allenes, and Related Compounds   Patai S. Wiley; New York: 1980.  p.363 

<A NAME="RU03006ST-1C">1c</A> Schuster HF. Coppola GM. Allenes in Organic Synthesis   Wiley; New York: 1984. 

<A NAME="RU03006ST-1D">1d</A> Yamamoto H. In Comprehensive Organic Synthesis   Vol. 2:  Trost MB. Fleming I. Pergamon; Oxford: 1991.  p.81 

<A NAME="RU03006ST-1E">1e</A> Modern Acetylene Chemistry   Stang PJ. Diederich F. VCH; Weinheim: 1995. 

<A NAME="RU03006ST-2A">2a</A> Mukaiyama T. Harada T. Chem. Lett.  1981,  621 

<A NAME="RU03006ST-2B">2b</A> Boldrini GP. Tagliavini E. Trombini C. Umani-Ronchi A. J. Chem. Soc., Chem. Commun.  1986,  685 

<A NAME="RU03006ST-2C">2c</A> Tanaka H. Hamatani T. Yamashita S. Torii S. Chem. Lett.  1986,  1461 

<A NAME="RU03006ST-2D">2d</A> Iyoda M. Kanao Y. Nishizaki M. Oda M. Bull. Chem. Soc. Jpn.  1989,  62:  3380 

<A NAME="RU03006ST-2E">2e</A> Belyk K. Rozema MJ. Knochel P. J. Org. Chem.  1992,  57:  4074 

<A NAME="RU03006ST-2F">2f</A> Yavari I. Riazi-Kermani F. Synth. Commun.  1995,  25:  2938 

<A NAME="RU03006ST-2G">2g</A> Houllemare D. Outurquin F. Paulmier C. J. Chem. Soc., Perkin Trans. 1  1997,  1629 

<A NAME="RU03006ST-2H">2h</A> Bieber LW. da Silva MF. da Costa RC. Silva LOS. Tetrahedron Lett.  1998,  39:  3655 

<A NAME="RU03006ST-2I">2i</A> Kundu A. Prabhakar S. Vairamani M. Roy S. Organometallics  1999,  18:  2782 

<A NAME="RU03006ST-2J">2j</A> Banerjee M. Roy S. Chem. Commun.  2003,  534 

<A NAME="RU03006ST-2K">2k</A> Banerjee M. Roy S. Org. Lett.  2004,  6:  2137 

For representative non-Barbier-type selective carbonyl allenylations and propargylations, see:

<A NAME="RU03006ST-3A">3a</A> Nokami J. Tamaoka T. Koguchi T. Okawara R. Chem. Lett.  1984,  1939 

<A NAME="RU03006ST-3B">3b</A> Suzuki M. Morita Y. Noyori R. J. Org. Chem.  1990,  55:  441 

<A NAME="RU03006ST-3C">3c</A> Brown HC. Khire UR. Narla G. Racherla US. J. Org. Chem.  1995,  60:  544 

<A NAME="RU03006ST-3D">3d</A> Kobayashi S. Nishio K. J. Am. Chem. Soc.  1995,  117:  6392 

<A NAME="RU03006ST-3E">3e</A> Marshall JA. Yu RH. Perkins JF. J. Org. Chem.  1995,  60:  5550 

<A NAME="RU03006ST-3F">3f</A> Marshall JA. Grant CM. J. Org. Chem.  1999,  64:  8214 

<A NAME="RU03006ST-3G">3g</A> Nakajima M. Saito M. Hashimoto S. Tetrahedron: Asymmetry  2002,  13:  2449 ; and references cited therein

For the preparation of allenyltin and propargyltin compounds, see:

<A NAME="RU03006ST-4A">4a</A> Guillemin J.-C. Malagu K. Organometallics  1999,  18:  5259 

<A NAME="RU03006ST-4B">4b</A> Kjellgren J. Sunden H. Szabo KJ. J. Am. Chem. Soc.  2005,  127:  1787 

<A NAME="RU03006ST-5">5</A> Lin MJ. Loh TP. J. Am. Chem. Soc.  2003,  125:  13042 

<A NAME="RU03006ST-6">6</A> Masuyama Y. Watabe A. Kurusu Y. Synlett  2003,  1713 

<A NAME="RU03006ST-7A">7a</A> Masuyama Y. Ito A. Fukuzawa M. Terada K. Kurusu Y. Chem. Commun.  1998,  2025 

<A NAME="RU03006ST-7B">7b</A> Masuyama Y. Watabe A. Ito A. Kurusu Y. Chem. Commun.  2000,  2009 

<A NAME="RU03006ST-8">8</A> For carbonyl allylation with SnI₄ and TBAI, see: Masuyama Y. Takeuchi K. Kurusu Y. Tetrahedron Lett.  2005,  46:  2861 

<A NAME="RU03006ST-9">9</A>

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).

<A NAME="RU03006ST-10A">10a</A> 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 

<A NAME="RU03006ST-10B">10b</A> 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