Arenesulfinamides as New Reagents for the Synthesis of Allylic Sulfoxides

Abstract

Reaction of arenesulfinamides with alkenes bearing ­allylic hydrogens in the presence of Yb(OTf)₃/TMSCl led to the corresponding allylic sulfoxides in good yields.

alkenes - sulfinamides - lanthanides - regioselectivity - sulfoxides

References

<A NAME="RD03604ST-1A">1a</A> Synthesis of Sulfones, Sulfoxides, and Cyclic Sulfides   Patai S. Rappoport Z. Wiley; Chichester: 1994. 

<A NAME="RD03604ST-1B">1b</A> Organosulfur Chemistry: Synthetic Aspects   Page P. Academic; London: 1995. 

<A NAME="RD03604ST-1C">1c</A> Cremlyn RJ. In An Introduction to Organosulfur Chemistry   Wiley-VCH; Weinheim: 1996. 

<A NAME="RD03604ST-1D">1d</A> Mikolajczk M. Drabowicz J. Kielbasinski P. In Chiral Sulfur Reagents: Applications in Asymmetric and Stereoselective Synthesis   Mikolajczk M. CRC Press; Boca Raton: 1996. 

<A NAME="RD03604ST-2A">2a</A> Davis FA. Zhou P. Chen BC. Chem. Soc. Rev.  1998,  27:  13 

<A NAME="RD03604ST-2B">2b</A> Ellman JA. Owens TD. Tang TP. Acc. Chem. Res.  2002,  35:  984 

<A NAME="RD03604ST-3A">3a</A> Borzilleri RM. Weinreb SM. Synthesis  1995,  347 

<A NAME="RD03604ST-3B">3b</A> Weinreb SM. Top. Curr. Chem.  1997,  190:  132 

<A NAME="RD03604ST-4">4</A> Davis FA. Qu J. Srirajan V. Joseph R. Titus DD. Heterocycles  2002,  58:  251 

Recently, this catalytic system has been reported to be highly efficient in the catalysis of imino ene reactions of N-tosyl-benzaldimine:

<A NAME="RD03604ST-5A">5a</A> Yamanaka M. Nishida A. Nakagawa M. Org. Lett.  2000,  2:  159 

<A NAME="RD03604ST-5B">5b</A> Yamanaka M. Nishida A. Nakagawa M. J. Org. Chem.  2003,  68:  3112 

<A NAME="RD03604ST-6">6</A> Evans DA. Andrews GC. Acc. Chem. Res.  1974,  7:  147 

<A NAME="RD03604ST-7A">7a</A> Annunziata R. Cinquini M. Cozzi F. Raimondi L. J. Chem. Soc., Chem. Commun.  1986,  366 

<A NAME="RD03604ST-7B">7b</A> Hua DH. Venkataraman S. Coulter MJ. Sinai-Zingde G. J. Org. Chem.  1987,  52:  719 

<A NAME="RD03604ST-7C">7c</A> Koprowski M. Krawczyk E. Skowroñska A. McPartlin M. Choi N. Radojevic S. Tetrahedron  2001,  57:  1105 

<A NAME="RD03604ST-7D">7d</A> Nokami J. Kataoka K. Shiraishi K. Osafune M. Hussain I. Sumida S. J. Org. Chem.  2001,  66:  1228 

<A NAME="RD03604ST-7E">7e</A> Kim T. Kim K. Park YJ. Eur. J. Org. Chem.  2002,  493 

<A NAME="RD03604ST-7F">7f</A> Chuard R. Giraud A. Renaud P. Angew. Chem. Int. Ed.  2002,  41:  4323 

<A NAME="RD03604ST-8A">8a</A> Hua DH. Sinai-Zingde G. Venkataraman S. J. Am. Chem. Soc.  1985,  107:  4088 

<A NAME="RD03604ST-8B">8b</A> Hua DH. J. Am. Chem. Soc.  1986,  108:  3835 

<A NAME="RD03604ST-8C">8c</A> Hua DH. Venkataraman S. Chan-Yu-King R. Paukstelis JV. J. Am. Chem. Soc.  1988,  110:  4741 

<A NAME="RD03604ST-8D">8d</A> Hua DH. Venkataraman S. Ostrander RA. Sinai G.-Z. McCann PJ. Coulter MJ. Xu MR. J. Org. Chem.  1988,  53:  507 

<A NAME="RD03604ST-9A">9a</A> Choi S. Yang JD. Ji M. Choi H. Kee M. Ahn K.-H. Byeon S.-H. Baik W. Koo S. J. Org. Chem.  2001,  66:  8192 

<A NAME="RD03604ST-9B">9b</A> Lidén AA. Krüger L. Bäckvall J.-E. J. Org. Chem.  2003,  68:  5890 

<A NAME="RD03604ST-10">10</A> Snider BB. J. Org. Chem.  1981,  46:  3155 

<A NAME="RD03604ST-11">11</A> Moissenkov AM. Dragan VA. Koptenkova VA. Veselovsky VV. Synthesis  1987,  814 

<A NAME="RD03604ST-12">12</A> Andersen KK. In Comprehensive Organic Chemistry   Barton D. Ollis WD. 1st ed., Vol. 3:  Jones N. Pergamon Press Ltd.; Oxford: 1979.  p.321 

Sulfinamides can be easily prepared by reaction of sulfinyl chlorides with NH₃, see:

<A NAME="RD03604ST-13A">13a</A> Andersen KK. In Comprehensive Organic Chemistry   Barton D. Ollis WD. 1st ed., Vol. 3:  Jones N. Pergamon Press Ltd.; Oxford: 1979.  p.326 

<A NAME="RD03604ST-13B">13b</A> Backes BJ. Dragoli DR. Ellman JA. J. Org. Chem.  1999,  64:  5472 

<A NAME="RD03604ST-14">14</A>

Typical Procedure for the Synthesis of Allylic Sulfoxides 3: To a solution of p-toluenesulfinamide 1a (0.15 g; 0.966 mmol) in dry CH₂Cl₂ (20 mL), Yb(OTf)₃ (0.30 g; 0.483 mmol), α-methyl styrene (0.34 g; 2.899 mmol) and TMSCl (0.11 g; 0.966 mmol) were sequentially added. After the addition, the reaction mixture was stirred at r.t. for 16 h. The inorganic salts were removed by filtration and the filtrate was collected. The solvent was evaporated to dryness and the residue purified by silica gel chromatography eluting with 1:3 to 1:1 EtOAc-hexanes. An analytically pure sample was obtained by recrystallization from Et₂O/n-pentane (white prisms). Yield (0.22 g, 90%); mp 63-65 °C. IR (neat): 1620, 1597, 1494, 1085, 1045, 810, 778, 701 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 2.38 (s, 3 H, CH ₃ ), 3.82 (d, 1 H, ² J = 12.7 Hz, CH ₂ SO), 4.07 (d, 1 H, ² J = 12.7 Hz, CH ₂ SO), 5.09 (s, 1 H, = CH ₂ ), 5.53 (s, 1 H, = CH ₂ ), 7.23-7.49 (m, 9 H, aromatics). ¹³C {¹H} NMR (50 MHz, CDCl₃): δ = 21.3 (q), 64.7 (t), 119.7 (t), 124.3 (2 × d), 126.0 (2 × d), 128.0 (d), 128.4 (2 × d), 129.5 (2 × d), 137.5 (s), 138.9 (s), 140.2 (s), 141.6 (s). Anal. Calcd for C₁₆H₁₆SO: C, 74.96; H, 6.29; S, 12.51. Found: C, 74.72; H, 6.47; S, 12.20.

<A NAME="RD03604ST-15A">15a</A> Thomas AF. Heathcock CH. ApSimon JW. Hooper JW. In The Total Synthesis of Natural Products   Vol 2:  ApSimon JW. Wiley; New York: 1973. 

<A NAME="RD03604ST-15B">15b</A> Savu PM. Katzenellenbogen JA. J. Org. Chem.  1981,  46:  239 

<A NAME="RD03604ST-15C">15c</A> Masaki Y. Hashimoto K. Kaji K. Tetrahedron  1984,  40:  3481 

<A NAME="RD03604ST-16">16</A> Knight DJ. Lin P. Russell ST. Whitham GH. J. Chem. Soc., Perkin Trans. 1  1987,  2701 

<A NAME="RD03604ST-17A">17a</A> Rautenstrauch V. J. Chem. Soc., Chem. Commun.  1970,  526 

<A NAME="RD03604ST-17B">17b</A> Wang W.-Y. Reusch W. Tetrahedron  1988,  44:  1007