Asymmetric Mukaiyama Aldol Reaction Catalyzed by C ₂-Symmetric N,N′-Dioxide-Ni(II) Complex

 

 Buy Article Permissions and Reprints All articles of this category

Abstract

The N,N′-dioxide-Ni(II) complex has been developed for the asymmetric Mukaiyama aldol reaction between glyoxal derivatives and enolsilane which produced the 2-hydroxy-1,4-dicarbonyl compounds in moderate to high yields (up to 95%) with excellent enantioselectivities (up to 95% ee). Based on the configuration of the product and X-ray structure of the catalyst, a possible transition state was proposed to explain the mechanism of the reaction.

References and Notes

• For reviews, see:
• 1a Gröger H. Vogl EM. Shibasaki M. Chem. Eur. J.  1998,  4:  1137 
  Google Scholar
• 1b Nelson SG. Tetrahedron: Asymmetry  1998,  9:  357 
  Google Scholar
• 1c Denmark SE. Stavenger RA. Acc. Chem. Res.  2000,  33:  432 
  Google Scholar
• 1d Palomo C. Oiarbide M. García JM. Chem. Eur. J.  2002,  8:  36 
  Google Scholar
• 1e Schetter B. Mahrwald R. Angew. Chem. Int. Ed.  2006,  45:  7506 
  Google Scholar
• 1f Adachi S. Harada T. Eur. J. Org. Chem.  2009,  3661 
  Google Scholar
• 1g Geary LM. Hultin PG. Tetrahedron: Asymmetry  2009,  20:  131 
  Google Scholar
• 2 Kobayashi S. Fujishita Y. Mukaiyama T. Chem. Lett.  1990,  1455 
  Google Scholar
• For selected examples, see:
• 3a Furuta K. Maruyama T. Yamamoto H. J. Am. Chem. Soc.  1991,  113:  1041 
  Google Scholar
• 3b Carreira EM. Singer RA. Lee W. J. Am. Chem. Soc.  1994,  116:  8837 
  Google Scholar
• 3c Mikami K. Matsukawa S. J. Am. Chem. Soc.  1994,  116:  4077 
  Google Scholar
• 3d Keck GE. Krishnamurthy D. J. Am. Chem. Soc.  1995,  117:  2363 
  Google Scholar
• 3e Krüger J. Carreira EM. J. Am. Chem. Soc.  1998,  120:  837 
  Google Scholar
• 3f Evans DA. Kozlowski MC. Murry JA. Burgey CS. Campos KR. Connell BT. Staples RJ. J. Am. Chem. Soc.  1999,  121:  669 
  Google Scholar
• 3g Yamashita Y. Ishitani H. Shimizu H. Kobayashi S. J. Am. Chem. Soc.  2002,  124:  3292 
  Google Scholar
• 3h Le JC.-D. Pagenkopf BL. Org. Lett.  2004,  6:  4097 
  Google Scholar
• 3i Oisaki K. Zhao D. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2006,  128:  7164 
  Google Scholar
• 3j Fu F. Teo YC. Loh TP. Tetrahedron Lett.  2006,  47:  4267 
  Google Scholar
• 3k Kiyooka S. Matsumoto S. Shibata T. Shinozaki K. Tetrahedron  2010,  66:  1806 ; and references therein
  Google Scholar
• For selected examples, see:
• 4a Denmark SE. Fan Y.
  J. Am. Chem. Soc.  2002,  124:  4233 
  Google Scholar
• 4b Denmark SE. Wynn T. Beutner GL. J. Am. Chem. Soc.  2002,  124:  13405 
  Google Scholar
• 4c Zhuang W. Poulsen TB. Jørgensen KA. Org. Biomol. Chem.  2005,  3:  3284 
  Google Scholar
• 4d McGilvra JD. Unni AK. Modi K. Rawal VH. Angew. Chem. Int. Ed.  2006,  45:  6130 
  Google Scholar
• 4e Adachi S. Harada T. Org. Lett.  2008,  10:  4999 
  Google Scholar
• 4f Gondi VB. Hagihara K. Rawal VH. Angew. Chem. Int. Ed.  2009,  48:  776 
  Google Scholar
• 4g García-García P. Lay F. García-García P. Rabalakos C. List B. Angew. Chem. Int. Ed.  2009,  48:  4363 
  Google Scholar
• 4h Cheon CH. Yamamoto H. Org. Lett.  2010,  12:  2476 ; and references therein
  Google Scholar
• 5a Evans DA. MacMillan DWC. Campos KR.
  J. Am. Chem. Soc.  1997,  119:  10859 
  Google Scholar
• 5b Evans DA. Burgey CS. Kozlowski MC. Tregay SW. J. Am. Chem. Soc.  1999,  121:  686 
  Google Scholar
• 5c Evans DA. Masse CE. Wu J. Org. Lett.  2002,  4:  3375 
  Google Scholar
• 5d Langner M. Bolm C. Angew. Chem. Int. Ed.  2004,  43:  5984 
  Google Scholar
• 5e Akullian LC. Snapper ML. Hoveyda AH. J. Am. Chem. Soc.  2006,  128:  6532 
  Google Scholar
• 5f Engers JL. Pagenkopf BL. Eur. J. Org. Chem.  2009,  6109 
  Google Scholar
• 5g Gondi VB. Hagihara K. Rawal VH. Chem. Commun.  2010,  46:  904 
  Google Scholar
• For reviews on N-dioxides in the asymmetric catalysis, see:
• 6a Chelucci G. Murineddu G. Pinna GA. Tetrahedron: Asymmetry  2004,  15:  1373 
  Google Scholar
• 6b Malkov AV. Kočovský P. Eur. J. Org. Chem.  2007,  29 
  Google Scholar
• For examples of our recent work, see:
• 7a Zheng K. Shi J. Liu XH. Feng XM. J. Am. Chem. Soc.  2008,  130:  15770 
  Google Scholar
• 7b Zheng K. Liu XH. Zhao JN. Yang Y. Lin LL. Feng XM. Chem. Commun.  2010,  46:  3771 
  Google Scholar
• 7c Xie MS. Chen XH. Zhu Y. Gao B. Lin LL. Liu XH. Feng XM. Angew. Chem. Int. Ed.  2010,  49:  3799 
  Google Scholar
• 7d Hui YH. Jiang J. Wang WT. Chen WL. Cai YF. Lin LL. Liu XH. Feng XM. Angew. Chem. Int. Ed.  2010,  49:  4290 
  Google Scholar
• 7e Li W. Wang J. Hu XL. Shen K. Wang WT. Chu YY. Lin LL. Liu XH. Feng XM. J. Am. Chem. Soc.  2010,  132:  8532 
  Google Scholar
• 8 Terada M. Soga K. Momiyama N. Angew. Chem. Int. Ed.  2008,  47:  4122 
  CrossrefPubMedGoogle Scholar

General Procedure for the Asymmetric Mukaiyama Aldol Reaction between Glyoxal Derivative 1a and Enolsilane 3a:
Ligand L7 (0.01 mmol) and Ni(BF₄)₂˙6H₂O (0.01 mmol) were dissolved in CH₂Cl₂ (0.5 mL) and stirred at 30 ˚C for 1 h. Then the solvent was removed and glyoxal derivative 1a (0.1 mmol) was added. After adding CH₂Cl₂ (1.0 mL) and enolsilane 3a (0.15 mmol), the mixture was stirred at 30 ˚C for 24 h under N₂ atmosphere. Then, THF (2.0 mL) and 1 N HCl (1.0 mL) were added to the reaction mixture. After stirring at r.t. for 30 min, this solution was poured into a separatory funnel and diluted with Et₂O (5.0 mL) and H₂O (1.0 mL). After mixing, the aqueous layer was discarded and the ether layer was washed with sat. aq NaHCO₃ (5.0 mL) and brine (5.0 mL). The resulting ether layer was dried over anhyd MgSO₄, and concentrated in vacuo. The crude product was chromatographed on silica gel to give the desired adduct 5a: 94% yield; 92% ee {determined by HPLC analysis with a Chiral OJ-H column, hexane-2-PrOH (80:20), 1.0 mL/min, UV = 254 nm; t _R1 = 18.6 min, t _R2 = 20.5 min); [α]_D ^²5 +11.9 (c 0.454, in CH₂Cl₂}; ^¹H NMR (400 MHz, CDCl₃): δ = 3.37-3.49 (m, 2 H), 4.04 (d, J = 6.0 Hz, 1 H), 5.68-5.73 (m, 1 H), 7.46-7.55 (m, 4 H), 7.58-7.66 (m, 2 H), 7.95-8.01 (m, 4 H) ppm.

• Supplementary Material