Phosphonium Salt Catalyzed Addition of Diethylzinc to Aldehydes

Abstract

The addition of diethylzinc to aromatic, heteroaromatic, and aliphatic aldehydes at room temperature is efficiently catalyzed by 1-7 mol% tetrabutylphosphonium chloride. The corresponding addition products are obtained in good to excellent yields of up to 99%. Moreover, polymer bond phosphonium salts can be used to catalyze this reaction with excellent recovery of the polymer bond catalyst up to three cycles. The application of chiral bifunctional phosphonium salts revealed a remarkable counter anion effect. Changing the anion, the activity of the tetrabutylphosphonium salt decreased in the order Cl^- > Br^- > I^- ≈ TsO^- > BF₄ ^- ≈ PF₆ ^-. However, the nature of the cation had also significant influence. Tetraalkyl­ammonium chlorides showed similar activity compared to phosphonium chlorides, while alkaline metal chlorides proved to be considerably less active.

Key words

catalysis - phosphonium salt - addition - diethylzinc - aldehydes

References

• 1a Frankland E. Justus Liebigs Ann. Chem.  1849,  71:  171 
• 1b Frankland E. Q. J. Chem. Soc.  1850,  2:  263 
• For the application of organozinc reagents in organic synthesis, see:
• 2a Knochel P. Singer RD. Chem. Rev.  1993,  93:  2117 
• 2b Erlik E. Organozinc Reagents in Organic Synthesis   CRC Press; Boca Raton: 1996. 
• 2c Knochel P. Almena Perea JJ. Jones P. Tetrahedron  1998,  54:  8275 
• For recent reviews, see:
• 3a Pu L. Yu H.-B. Chem. Rev.  2001,  101:  757 
• 3b Brunel JM. Chem. Rev.  2005,  105:  857 
• 3c Yus M. Ramon DJ. Pure Appl. Chem.  2005,  77:  2111 
• 3d Hatano M. Miyamoto T. Ishihara K. Curr. Org. Chem.  2007,  11:  127 
• 3e Denmark SE. Beutner GL. Angew. Chem. Int. Ed.  2008,  47:  1560 ; Angew. Chem. 2008, 120, 1584
• 3f Hatano M. Ishihara K. Chem. Rec.  2008,  8:  143 
• 3g Hatano M. Ishihara K. Synthesis  2008,  1647 
• 3h Dimitrov V. Kamenova-Nacheva M. J. Univ. Chem. Tech. Metall.  2009,  44:  317 
• For examples on recent developments, see:
• 4a Rudolph J. Lormann M. Bolm C. Dahmen S. Adv. Synth. Catal.  2005,  347:  1361 
• 4b Schmidt F. Rudolph J. Bolm C. Adv. Synth. Catal.  2007,  349:  703 
• 4c Burguete MI. Collado M. Escorihuela J. Luis Santiago V. Angew. Chem. Int. Ed.  2007,  46:  9002 ; Angew. Chem. 2007, 119, 9160
• 4d Milburn RR. Hussain SMS. Prien O. Ahmed Z. Snieckus V. Org. Lett.  2007,  9:  4403 
• 4e Lombardo M. Chiarucci M. Trombini C. Chem. Eur. J.  2008,  14:  11288 
• 4f Jimeno C. Sayalero S. Fjermestad T. Colet G. Maseras F. Pericàs M. Angew. Chem. Int. Ed.  2008,  47:  1098 ; Angew. Chem. 2008, 120, 1114
• 4g Binder CM. Bautista A. Zaidlewicz M. KrzeminÌnski MP. Oliver A. Singaram B. J. Org. Chem.  2009,  74:  2337 
• 5 Lewis Acids in Organic Synthesis   Yamamoto H. Wiley-VCH; Weinheim: 2000. 
• For recent reviews on Lewis acidic organocatalysts, see:
• 6a Werner T. Adv. Synth. Catal.  2009,  351:  1469 
• 6b List B. Sereda O. Tabassum S. Wilhelm R. Top. Curr. Chem.  2009,  291:  349 
• 7a Chen C.-T. Chao S.-D. Yen K.-C. Chen C.-H. Chou I.-C. Hon S.-W. J. Am. Chem. Soc.  1997,  119:  11341 
• 7b Chen C.-T. Chao S.-D. Yen K.-C. Synlett  1998,  924 
• 8a Zhou H. Campbell EJ. Nguyen ST. Org. Lett.  2001,  3:  2229 
• 8b Jurcík V. Wilhelm R. Tetrahedron: Asymmetry  2006,  17:  801 
• 8c Jurcik V. Wilhelm R. Org. Biomol. Chem.  2005,  3:  239 
• 9a Howarth J. Hanlon K. Fayne D. McCormac P. Tetrahedron Lett.  1997,  38:  3097 
• 9b Ranu BC. Banerjee S. Das A. Tetrahedron Lett.  2006,  47:  881 
• 9c Zheng ZQ. Wang J. Wu TH. Zhou XP. Adv. Synth. Catal.  2007,  349:  1095 
• 10a Mukaiyama T. Matsui S. Kashiwagi K. Chem. Lett.  1989,  993 
• 10b Mukaiyama T. Kashiwagi K. Matsui S. Chem. Lett.  1989,  1397 
• 10c Terada M. Kouchi M. Tetrahedron  2006,  62:  401 
• 11a Chastrette M. Amouroux R. Tetrahedron Lett.  1970,  5165 
• 11b Soai K. Watanabe M. J. Chem. Soc., Chem. Commun.  1990,  43 
• 11c Musser CA. Richey HG. J. Org. Chem.  2000,  65:  7750 
• 11d McNulty J. Dyck J. Larichev V. Capretta A. Robertson AJ. Lett. Org. Chem.  2004,  1:  137 
• 12 Fischer S. Groth U. Jeske M. Schütz T. Synlett  2002,  1922 
• 13 Kinder FR. Jarosinski MA. Anderson WK. J. Org. Chem.  1991,  56:  6475 
• 14 Leglaye P. Donnadieu B. Brunet J.-J. Chauvin R. Tetrahedron Lett.  1998,  39:  9179 
• 16a Wang X. Tian S.-K. Tetrahedron Lett.  2007,  48:  6010 
• 16b Amurrio I. Cordoba R. Csaky AG. Plumet J. Tetrahedron  2004,  60:  10521 
• 16c Cordoba R. Plumet J. Tetrahedron Lett.  2003,  44:  6157 
• 17a For a review on halide effects in transition-metal catalysis, see: Fagnou K. Lautens M. Angew. Chem. Int. Ed.  2002,  41:  26 ; Angew. Chem. 2002, 114, 26
• 17b For a recent example on anion effects in the addition of Et₂Zn to benzaldehyde, see: von Rönn R. Christoffers J. Tetrahedron  2011,  67:  334 
• 18 Kneisel FF. Dochnahl M. Knochel P. Angew. Chem. Int. Ed.  2004,  43:  1017 ; Angew. Chem. 2004, 116, 1032
• 19 Imada Y. Kitagawa T. Ohno T. Iida H. Naota T. Org. Lett.  2010,  12:  32 
• 20 Cobb AJA. Marson CM. Tetrahedron  2005,  61:  1269 
• 21 Occhialini D. Kristensen JS. Daasbuerg K. Lund H. Acta Chem. Scand.  1992,  46:  474 
• 22 Hatano M. Miyamoto T. Ishihara K. J. Org. Chem.  2006,  71:  6474 
• 23 Yang X.-F. Hirose T. Zhang G.-Y. Tetrahedron: Asymmetry  2008,  19:  1670 
• 24 Seebach D. Beck AK. Schmidt B. Wang YM. Tetrahedron  1994,  50:  4363 
• 25 Perez-Prieto J. Galian RE. Burgos PO. del Carmen Morant Minana M. Miranda MA. Lopez-Ortiz F. Org. Lett.  2005,  7:  3869 
• 26 Uenishi J.-i. Hiraoka T. Hata S. Nishiwaki K. Yonemitsu O. Nakamura K. Tsukube H. J. Org. Chem.  1998,  63:  2481 
• 27 Findlay NJ. Park SR. Schoenebeck F. Cahard E. Zhou S. Berlouis LEA. Spicer MD. Tuttle T. Murphy JA. J. Am. Chem. Soc.  2010,  132:  15462 
• 28 Runge MB. Mwangi MT. Miller AL. Perring M. Bowden NB. Angew. Chem. Int. Ed.  2008,  47:  935 ; Angew. Chem. 2008, 120, 949
• 29 Maytum HC. Francos J. Williams JMJ. Whatrup DJ. Chem. Asian J.  2010,  5:  538 
• 30 Cutulic SPY. Findlay NJ. Zhou S. Chrystal EJT. Murphy JA. J. Org. Chem.  2009,  74:  8713 

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[(2S)-3-Hydroxy-2-methylpropyl](triphenyl)phosphonium bromide (9) was purchased from Sigma-Aldrich.