SnCl₂/KI-Mediated Allylation Reactions of Formaldehyde in Water

Abstract

An efficient procedure for SnCl₂/KI-mediated allylation reactions of formaldehyde with a variety of allylic bromides in aqueous solution is reported. Under conditions developed in this effort, various homoallylic alcohols and 2-halohomoallylic alcohols are produced in good to excellent yields.

Key words

SnCl₂/KI-mediated allylation reactions - aqueous solution - formaldehyde - homoallylic alcohols - 2-halohomoallylic alcohols

References and Notes

• 1a Snider BB. Rodini DJ. Kirk TC. Cordova R.
  J. Am. Chem. Soc.  1982,  104:  555 
• 1b Maruoka K. Concepcion AB. Hirayama N. Yamamoto H. J. Am. Chem. Soc.  1990,  112:  7422 
• 1c Lecomte V. Bolm C. Adv. Synth. Catal.  2005,  347:  1666 
• 1d Cesario C. Miller MJ. Tetrahedron Lett.  2010,  51:  3050 ; and references cited therein
• 2a Trost BM. Papillon JPN. Nussbaumer T. J. Am. Chem. Soc.  2005,  127:  17921 
• 2b Kim DS. Dong CG. Kim JT. Guo H. Huang J. Tiseni PS. Kishi Y. J. Am. Chem. Soc.  2009,  131:  15636 
• 3 Metal-Catalyzed Cross-Coupling Reactions   2nd ed.:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 
• 4 Corey EJ. Yu C.-M. Kim SS. J. Am. Chem. Soc.  1989,  111:  5495 
• 5 Mandai T. Nokami J. Yano T. Yoshinaga Y. Otera J. J. Org. Chem.  1984,  49:  172 
• 6 Kurosu M. Lin M.-H. Kishi Y. J. Am. Chem. Soc.  2004,  126:  12248 
• 7 Einhorn C. Luche J.-L. J. Organomet. Chem.  1987,  322:  177 
• 8 Nokami J. Tamaoka T. Ogawa H. Wakabayashi S. Chem. Lett.  1986,  541 
• 9 Loh TP. Li XR. Angew. Chem., Int. Ed. Engl.  1997,  36:  980 
• 10 Paquette LA. Bennett GD. Isaac MB. Chhatriwalla A. J. Org. Chem.  1998,  63:  1836 
• 11a Li CJ. Chem. Rev.  2005,  105:  3095 
• 11b Lindström UM. Chem. Rev.  2002,  102:  2751 
• 11c Chan TH. Issac BM. Pure Appl. Chem.  1996,  68:  919 
• 11d Li CJ. Tetrahedron  1996,  52:  5643 
• 11e Li CJ. Chan TH. Organic Reactions in Aqueous Media   John Wiley & Sons, Inc.; New York: 1997. 
• 11f Paquette LA. In Green Chemistry: Frontiers in Benign Chemical Synthesis and Processing   Anastas P. Williamson T. Oxford University Press; New York: 1998. 
• 12a Pereyre M. Quintard MJ.-P. Rahm A. Tin in Organic Synthesis   Butterworth; London: 1987. 
• 12b Smith PJ. Toxicological Data on Organotin Compounds   International Tin Research Institute; London: 1978. 
• 13 Screening conditions include allylic bromide 1b with Sn in Et₂O-H₂O, Sn/HBr in H₂O, SnCl₂/Al in H₂O, SnCl₂/Zn in H₂O, In in THF-H₂O, and SnCl₂/KI in H₂O
• 14a Houllemare D. Outurquin F. Paulmier C. J. Chem. Soc., Perkin Trans. 1  1997,  1629 
• 14b Gremyachinskiy DE. Smith LL. Gross PH. Samoshin VV. Green Chem.  2002,  4:  317 
• 14c Samoshin VV. Gremyachinskiy DE. Smith LL. Bliznets IV. Gross PH. Tetrahedron Lett.  2002,  43:  6329 
• 14d Lin M.-H. Hung S.-F. Lin L.-Z. Tsai W.-S. Chuang T.-H. Org. Lett.  2011,  13:  332 
• 15 Tsuji T. Usugi S. Yorimitsu H. Shinokubo H. Matsubara S. Oshima K. Chem. Lett.  2002,  1:  2 

16

General Procedure for SnCl₂/KI-Mediated Allylation Reactions of Formaldehyde
A mixture of formaldehyde (82 mg, 1.0 mmol, 37 wt% aq solution), the allylating agent 2 (1.5 mmol), tin chloride dihydrate (339 mg, 1.5 mmol), and KI (249 mg, 1.5 mmol) in H₂O (2 mL) was stirred at r.t. overnight. The mixture was extracted with CH₂Cl₂ (3 × 5 mL). The combined organic layers were dried over Na₂SO₄ and concentrated in vacuo. The residue was subjected to silica gel chromatography by using Et₂O-hexanes (1:9) as eluent to give the product 1.