Prev. Article Next Article Table of Contents

Letter

Sodium Phenoxide−Phosphine Oxides as Extremely Active Lewis Base Catalysts for the Mukaiyama Aldol Reaction with Ketones

Your current credentials do not allow retrieval of the full text.

Purchase the full-text

PDF/HTML,
figures/images,
references and tables,
(where available)

Manabu Hatano, Eri Takagi, and Kazuaki Ishihara*

Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya, 464-8603, Japan

Org. Lett., 2007, 9 (22), pp 4527–4530

DOI: 10.1021/ol702052r

Publication Date (Web): September 26, 2007

Section:

General Organic Chemistry

Abstract

A highly efficient Mukaiyama aldol reaction between ketones and trimethylsilyl enolates catalyzed by sodium phenoxide−phosphine oxides as simple homogeneous Lewis base catalysts (0.5−10 mol %) was developed, which minimized competing retro-aldol reaction. For a variety of aromatic ketones and aldimines, aldol and Mannich-type products with an α-quaternary carbon center were obtained in good to excellent yields. Up to 100 mmol scale of benzophenone and trimethylsilyl enolate with 0.5 mol % of catalyst was established in 97% yield (34.8 g).

View: Full Text HTML | Hi-Res PDF | PDF w/ Links

Citing Articles

View all 31 citing articles

Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.

This article has been cited by 10 ACS Journal articles (5 most recent appear below).

Direct Catalytic Enantio- and Diastereoselective Aldol Reaction of Thioamides
Mitsutaka Iwata, Ryo Yazaki, I-Hon Chen, Devarajulu Sureshkumar, Naoya Kumagai, and Masakatsu Shibasaki
Journal of the American Chemical Society2011 133 (14), 5554-5560
- Direct Catalytic Enantio- and Diastereoselective Aldol Reaction of Thioamides
  Mitsutaka Iwata, Ryo Yazaki, I-Hon Chen, Devarajulu Sureshkumar, Naoya Kumagai, and Masakatsu Shibasaki
  Journal of the American Chemical Society2011 133 (14), 5554-5560
  A direct catalytic asymmetric aldol reaction of thioamides using a soft Lewis acid/hard Brønsted base cooperative catalyst comprising (R,R)-Ph-BPE/[Cu(CH3CN)4]PF6/LiOAr is described. Exclusive enolate generation from thioacetamides through a soft−soft ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Alkaline Earth Metal Catalysts for Asymmetric Reactions
Shu̅ Kobayashi and Yasuhiro Yamashita
Accounts of Chemical Research2011 44 (1), 58-71
- Alkaline Earth Metal Catalysts for Asymmetric Reactions
  Shu̅ Kobayashi and Yasuhiro Yamashita
  Accounts of Chemical Research2011 44 (1), 58-71
  The group 2 alkaline earth metals calcium (Ca), strontium (Sr), and barium (Ba) are among the most common elements on Earth, abundant in both the sea and the Earth’s crust. Although they are familiar in our daily lives, their application to organic ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Carbon Acid Induced Mukaiyama Aldol Type Reaction of Sterically Hindered Ketones
Hikaru Yanai, Yasuhiro Yoshino, Arata Takahashi and Takeo Taguchi
The Journal of Organic Chemistry2010 75 (15), 5375-5378
- Carbon Acid Induced Mukaiyama Aldol Type Reaction of Sterically Hindered Ketones
  Hikaru Yanai, Yasuhiro Yoshino, Arata Takahashi and Takeo Taguchi
  The Journal of Organic Chemistry2010 75 (15), 5375-5378
  1,1,3,3-Tetrakis(trifluoromethanesulfonyl)propane (Tf2CHCH2CHTf2) is one of the most effective Brønsted acid precatalysts for the Mukaiyama aldol type reactions of sterically hindered ketones. By using Tf2CHCH2CHTf2 in a range from 0.5 to 2.0 mol %, the ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Direct Catalytic Asymmetric Addition of Allyl Cyanide to Ketones via Soft Lewis Acid/Hard Brønsted Base/Hard Lewis Base Catalysis
Ryo Yazaki, Naoya Kumagai and Masakatsu Shibasaki
Journal of the American Chemical Society2010 132 (15), 5522-5531
- Direct Catalytic Asymmetric Addition of Allyl Cyanide to Ketones via Soft Lewis Acid/Hard Brønsted Base/Hard Lewis Base Catalysis
  Ryo Yazaki, Naoya Kumagai and Masakatsu Shibasaki
  Journal of the American Chemical Society2010 132 (15), 5522-5531
  We report that a hard Lewis base substantially affects the reaction efficiency of direct catalytic asymmetric γ-addition of allyl cyanide (1a) to ketones promoted by a soft Lewis acid/hard Brønsted base catalyst. Mechanistic studies have revealed that Cu/(...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Construction of Contiguous Tetrasubstituted Chiral Carbon Stereocenters via Direct Catalytic Asymmetric Aldol Reaction of α-Isothiocyanato Esters with Ketones
Tatsuhiko Yoshino, Hiroyuki Morimoto, Gang Lu, Shigeki Matsunaga and Masakatsu Shibasaki
Journal of the American Chemical Society2009 131 (47), 17082-17083
- Construction of Contiguous Tetrasubstituted Chiral Carbon Stereocenters via Direct Catalytic Asymmetric Aldol Reaction of α-Isothiocyanato Esters with Ketones
  Tatsuhiko Yoshino, Hiroyuki Morimoto, Gang Lu, Shigeki Matsunaga and Masakatsu Shibasaki
  Journal of the American Chemical Society2009 131 (47), 17082-17083
  Construction of contiguous tetrasubstituted chiral carbon stereocenters via direct catalytic asymmetric aldol reaction of α-substituted α-isothiocyanato esters with unactivated simple ketones is described. A Bu2Mg/Schiff base catalyst promoted the aldol ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links