^¹³ C NMR Analysis as a Useful Tool for Structural Assignment of Vinyl- and Dienyltin Derivatives

Abstract

During the last decade, vinyl- and dienyltin derivatives have been extensively developed and used in organic synthesis. ¹H NMR analysis of these compounds was the first analytical tool employed, together with ¹¹⁹Sn NMR, for the assignment of the E or Z stereochemistry of vinylstannyl derivatives. In this paper we want to show that ¹³C NMR is a powerful tool for structural analysis of vinyl- and dienyltin compounds. Chemical shifts and ¹³C-^119-117Sn coupling constants are reported for several examples. In all cases described, the ^³ J ¹³C _- ^119-117Sn values give the most definitive argument for structural assignment. ^¹ J, ^² J and ^³ J ¹³C-^119-117Sn coupling constants are also reported, along with the α, β, γ, and δ effects of the stannyl group. When the vinyltin function is functionalized with a heteroatomic substituant, some important changes occur in the chemical shifts and coupling constants. Some examples are given in the α-oxygen, -sulfur, -halogen, -silyl, and -tin substituted vinyltin series.

vinyltin - dienyltin - chemical shifs - coupling constants - heterosubstituted vinyltin

References

<A NAME="RA27301ST-1">1</A> Pereyre M. Quintard J.-P. Rahm A. Tin in Organic Synthesis   Butterworths; London: 1987. 

<A NAME="RA27301ST-2A">2a</A> Dodrell D. Burfitt I. Kitching W. Bullpitt M. Lee CH. Mynott RJ. Considine JL. Kuivlila HG. Sarma RH. J. Am. Chem. Soc.  1974,  96:  1640 

<A NAME="RA27301ST-2B">2b</A> Kitching W. Org. Magn. Reson.  1982,  20:  123 

<A NAME="RA27301ST-2C">2c</A> Rahm A. Grimeau J. Petraud M. Barbe B. J. Organomet. Chem.  1985,  286:  297 

<A NAME="RA27301ST-3A">3a</A> Smith PJ. Tupciauskas A. Annual Reports on NMR Spectroscopy   Vol. 8, Chemical Shifts of ¹¹9Sn Nuclei in Organotin Compounds:  Webb GA. Academic Press; New York: 1978.  p.291 

<A NAME="RA27301ST-3B">3b</A> Wrackmeyer B. Annual Reports on NMR Spectroscopy   Vol. 16, ¹¹9Sn-NMR Parameters:  Webb GA. Academic Press; New York: 1985.  p.73 

<A NAME="RA27301ST-3C">3c</A> Petrosyan VS. Progress in Nuclear Magnetic Resonance Spectroscopy   Vol. 11, NMR Spectra and Structures of Organotin Compounds:  Emsley JW. Feeney J. Sutcliffe LH. Pergamon Press; New York: 1976.  115. p.1976 

<A NAME="RA27301ST-3D">3d</A> Mitchell TN. Nettelbeck C. Magn. Reson. Chem.  1987,  25:  879 

<A NAME="RA27301ST-3E">3e</A> Wrackmeyer B. Guldner G. Abu-Orabi ST. Tetrahedron  1989,  45:  1119 

<A NAME="RA27301ST-3F">3f</A> Denmark SE. Weber EJ. Wilson TM. Tetrahedron  1989,  45:  1053 

<A NAME="RA27301ST-3G">3g</A> Nativi C. Taddeï M. Tetrahedron  1989,  45:  1131 

<A NAME="RA27301ST-4">4</A> Quintard J.-P. Degueil-Castaing M. Dumartin G. Barbe B. Petraud M. J. Organomet. Chem.  1982,  234:  270 ; and references therein

<A NAME="RA27301ST-5">5</A> Singh GJ. J. Organomet. Chem.  1975,  99:  251 

<A NAME="RA27301ST-6A">6a</A> Leusink AJ. Marsman JW. Budding HA. Noltes JG. Van Der Kerk GJM. Recl. Trav. Chim. Pays-Bas  1965,  84:  567 

<A NAME="RA27301ST-6B">6b</A> Leusink AJ. Marsman JW. Budding HA. Recl. Trav. Chim. Pays-Bas  1965,  84:  689 

<A NAME="RA27301ST-6C">6c</A> Leusink AJ. Budding HA. Marsman JW. J. Organomet. Chem.  1967,  9:  285 

<A NAME="RA27301ST-6D">6d</A> Leusink AJ. Budding HA. Drenth W. J. Organomet. Chem.  1967,  9:  295 

<A NAME="RA27301ST-7">7</A>

Practical information: in general the central ¹H signal is associated with two satellites corresponding to both ¹¹⁹Sn and ¹¹⁷Sn isotopes (for J ¹H-^119,117Sn > 70.0-100.0 Hz) but when J ¹H ^119,117Sn < 70.0-100.0 Hz, the two pairs of satellites are unresolved and only one coupling constant can be measured.

<A NAME="RA27301ST-8A">8a</A> Breitmaier E. Woelter W. Carbon- ¹³ NMR Spectroscopy   3rd ed.:  VCH; New York: 1987. 

<A NAME="RA27301ST-8B">8b</A> Stothers JB. Carbon- ¹³ NMR Spectroscopy   Academic Press; London: 1972. 

<A NAME="RA27301ST-9A">9a</A> Mitchell TN. J. Organomet. Chem.  1973,  59:  189 

<A NAME="RA27301ST-9B">9b</A> Kuivila HG. Considine JL. Sarma RH. Minott RJ. J. Organomet. Chem.  1976,  111:  179 

<A NAME="RA27301ST-9C">9c</A> Mitchell TN. Org. Magn. Reson.  1976,  8:  34 

<A NAME="RA27301ST-10">10</A> Ardisson J. Férézou J.-P. Li Y. Liu LW. Pancrazi A. Bull. Soc. Chim. Fr.  1992,  129:  401 

<A NAME="RA27301ST-11">11</A> Betzer J.-F. Delaloge F. Muller B. Pancrazi A. Prunet J. J. Org. Chem.  1997,  62:  7768 

<A NAME="RA27301ST-12">12</A> Barabas A. Botar AA. Gocan A. Popovici N. Hodosan F. Tetrahedron  1978,  34:  2191 

<A NAME="RA27301ST-13">13</A> Jacobs MF. Suthers BD. Hübener A. Kitching W. J. Chem. Soc., Perkin Trans. 1  1995,  901 

<A NAME="RA27301ST-14A">14a</A> Grover SH. Stothers JB. Can. J. Chem.  1974,  52:  870 

<A NAME="RA27301ST-14B">14b</A> Beierbeck H. Saunders JK. Can. J. Chem.  1976,  54:  2985 

<A NAME="RA27301ST-15">15</A> Thibonnet J. Launay V. Abarbri M. Duchêne A. Parrain J.-L. Tetrahedron Lett.  1998,  39:  4277 

<A NAME="RA27301ST-16A">16a</A> Launay V. Beaudet I. Quintard J.-P. Synlett  1997,  821 

<A NAME="RA27301ST-16B">16b</A> Launay V. Beaudet I. Quintard J.-P. Bull. Soc. Chim. Fr.  1997,  134:  937 

<A NAME="RA27301ST-16C">16c</A> Suzenet F. Parrain J.-L. Quintard J.-P. Eur. J. Org. Chem.  1999,  2957 

<A NAME="RA27301ST-16D">16d</A> Parrain J.-L. Beaudet I. Duchêne A. Watrelot S. Quintard J.-P. Tetrahedron Lett.  1993,  3 4:  5445 

<A NAME="RA27301ST-16E">16e</A> Beaudet I. Parrain J.-L. Quintard J.-P. Tetrahedron Lett.  1991,  32:  6333 

<A NAME="RA27301ST-16F">16f</A> Parrain J.-L. Duchêne A. Quintard J.-P. Tetrahedron Lett.  1990,  31:  1857 

<A NAME="RA27301ST-16G">16g</A> Suzenet F. PhD Thesis   Nantes; France: 1998. 

<A NAME="RA27301ST-17A">17a</A> Férézou J.-P. Julia M. Li Y. Liu LW. Pancrazi A. Synlett  1990,  766 

<A NAME="RA27301ST-17B">17b</A> Férézou J.-P. Julia M. Li Y. Liu LW. Pancrazi A. Synlett  1991,  614 

<A NAME="RA27301ST-17C">17c</A> Férézou J.-P. Julia M. Li Y. Liu LW. Pancrazi A. Porteu F. Bull. Soc. Chim. Fr.  1994,  131:  865 

<A NAME="RA27301ST-17D">17d</A> Férézou J.-P. Julia M. Li Y. Liu LW. Pancrazi A. Bull. Soc. Chim. Fr.  1995,  132:  428 

<A NAME="RA27301ST-18A">18a</A> Ardisson J. Férézou J.-P. Julia M. Pancrazi A. Tetrahedron Lett.  1987,  28:  2001 

<A NAME="RA27301ST-18B">18b</A> Ardisson J. Férézou J.-P. Julia M. Li Y. Liu LW. Pancrazi A. Bull. Soc. Chim. Fr.  1992,  129:  387 

<A NAME="RA27301ST-19A">19a</A> Betzer J.-F. Lallemand JY. Pancrazi A. Synthesis  1998,  522 

<A NAME="RA27301ST-19B">19b</A> Betzer J.-F. Ardisson J. Lallemand J.-Y. Pancrazi A. Tetrahedron Lett.  1997,  38:  2279 

<A NAME="RA27301ST-20">20</A> Betzer J.-F. Pancrazi A. Synthesis  1999,  629 

<A NAME="RA27301ST-21A">21a</A> Anies C. Pancrazi A. Lallemand J.-Y. Bull. Soc. Chim. Fr.  1997,  134:  183 

<A NAME="RA27301ST-21B">21b</A> Anies C. Pancrazi A. Lallemand J.-Y. Prangé T. Bull. Soc. Chim. Fr.  1997,  134:  203 

<A NAME="RA27301ST-21C">21c</A> Anies C. Billot L. Lallemand J.-Y. Pancrazi A. Tetrahedron Lett.  1995,  40:  7247 

<A NAME="RA27301ST-22">22</A> Khrimyan AP. Garibyan OA. Panosyan GA. Mailyan NS. Kinoyan FS. Makaryan GM. Bananyan SO. Russ. J. Org. Chem.  1993,  29:  1961 

<A NAME="RA27301ST-23">23</A> Betzer J.-F. Pancrazi A. Synlett  1998,  1129 

<A NAME="RA27301ST-24A">24a</A> Le Menez P. Fargeas V. Poisson J. Ardisson J. Lallemand J.-Y. Pancrazi A. Tetrahedron Lett.  1994,  42:  7767 

<A NAME="RA27301ST-24B">24b</A> Le Menez P. Firmo N. Fargeas V. Ardisson J. Pancrazi A. Synlett  1994,  995 

<A NAME="RA27301ST-24C">24c</A> Le Menez P. Berque I. Fargeas V. Ardisson J. Pancrazi A. Synlett  1994,  998 

<A NAME="RA27301ST-24D">24d</A> Le Menez P. Fargeas V. Berque I. Poisson J. Ardisson J. Lallemand J.-Y. Pancrazi A. J. Org. Chem.  1995,  60:  3592 

<A NAME="RA27301ST-24E">24e</A> Fargeas V. Le Menez P. Berque I. Ardisson J. Pancrazi A. Tetrahedron  1996,  52:  6613 

<A NAME="RA27301ST-25">25</A> Thibonnet J. PhD Thesis   Faculté des Sciences et Techniques, Tours; France: 1999. 

<A NAME="RA27301ST-26">26</A> Casson S. Kocienski P. Synthesis  1993,  1133 

<A NAME="RA27301ST-27A">27a</A> Magriotis PA. Doyle TJ. Kim KD. Tetrahedron Lett.  1990,  31:  2541 

<A NAME="RA27301ST-27B">27b</A> Magriotis PA. Brown JT. Scott ME. Tetrahedron Lett.  1991,  32:  5047 

<A NAME="RA27301ST-27C">27c</A> Magriotis PA. Scott ME. Kim KD. Tetrahedron Lett.  1991,  32:  6085 

<A NAME="RA27301ST-28">28</A> Pimm A. Kocienski P. Street SDA. Synlett  1992,  886 

<A NAME="RA27301ST-29">29</A>

Le Menez, P.; Brion, J.-D.; Pancrazi, A.; Ardisson, J. unpublished results.

<A NAME="RA27301ST-30">30</A> Petrosyan VS. Progress in Nuclear Magnetique Resonance Spectroscopy   Vol. 11:  Emsley JW. Feeney J. Sutcliffe LH. Pergamon Press; New York: 1976. 

<A NAME="RA27301ST-31">31</A> Lautens M. Huboux AH. Tetrahedron Lett.  1990,  31:  3105 

<A NAME="RA27301ST-32">32</A> Mitchell TN. Wickenkamp R. Amamria A. Dicke R. Schneider U. J. Org. Chem.  1987,  52:  4868 

<A NAME="RA27301ST-33A">33a</A> Mitchell TN. Amamria A. J. Organomet. Chem.  1983,  252:  47 

<A NAME="RA27301ST-33B">33b</A> Mitchell TN. Nettelbeck C. Mag. Reson. Chem.  1987,  25:  879 

<A NAME="RA27301ST-34">34</A> Piers E. Tillyer RD. Can. J. Chem.  1996,  74:  2048 

<A NAME="RA27301ST-35">35</A> Piers E. Skerlj RT. Can. J. Chem.  1994,  72:  2468 

<A NAME="RA27301ST-36">36</A> Suzenet F. Blart E. Quintard J.-P. Synlett  1998,  879