Title: Base‐Catalyzed Direct Aldolization of α‐Alkyl‐α‐Hydroxy Trialkyl Phosphonoacetates
Abstract: Angewandte Chemie International EditionVolume 51, Issue 19 p. 4685-4689 Communication Base-Catalyzed Direct Aldolization of α-Alkyl-α-Hydroxy Trialkyl Phosphonoacetates† Michael T. Corbett, Michael T. Corbett Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA)Search for more papers by this authorDr. Daisuke Uraguchi, Dr. Daisuke Uraguchi Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan)Search for more papers by this authorProf. Dr. Takashi Ooi, Corresponding Author Prof. Dr. Takashi Ooi [email protected] Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan) Takashi Ooi, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan) Jeffrey S. Johnson, Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA)Search for more papers by this authorProf. Dr. Jeffrey S. Johnson, Corresponding Author Prof. Dr. Jeffrey S. Johnson [email protected] Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA) Takashi Ooi, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan) Jeffrey S. Johnson, Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA)Search for more papers by this author Michael T. Corbett, Michael T. Corbett Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA)Search for more papers by this authorDr. Daisuke Uraguchi, Dr. Daisuke Uraguchi Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan)Search for more papers by this authorProf. Dr. Takashi Ooi, Corresponding Author Prof. Dr. Takashi Ooi [email protected] Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan) Takashi Ooi, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan) Jeffrey S. Johnson, Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA)Search for more papers by this authorProf. Dr. Jeffrey S. Johnson, Corresponding Author Prof. Dr. Jeffrey S. Johnson [email protected] Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA) Takashi Ooi, Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho B2-3(611), Chikusa, Nagoya 464-8603 (Japan) Jeffrey S. Johnson, Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599 (USA)Search for more papers by this author First published: 04 April 2012 https://doi.org/10.1002/anie.201200559Citations: 97 † The project described was supported by the National Institute of General Medical Sciences (Award R01 GM084927), the NEXT program, and a Grant-in-Aid for Scientific Research on Innovative Areas "Advanced Molecular Transformations by Organocatalysts" from MEXT. M.T.C. acknowledges a JSPS/NSF EAPSI Fellowship and the Global COE program in Chemistry of Nagoya University. Additional support from Novartis is gratefully acknowledged. X-ray crystallographic analysis was performed by Yusuke Ueki of Nagoya University. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Pass the P: Catalytic direct aldol addition of α-hydroxy trialkyl phosphonacetates to aldehydes affords α-hydroxy-β-phosphonyloxy ester products (see scheme). The fully substituted glycolate enolate intermediate is generated in situ under mild conditions by a [1,2] phosphonate–phosphate rearrangement. High enantioselectivity and dramatic enhancement of reaction diastereocontrol is realized by the application of chiral iminophosphorane catalysts. Supporting Information Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Filename Description anie_201200559_sm_miscellaneous_information.pdf21.8 MB miscellaneous_information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1B. M. Trost, C. S. Brindle, Chem. Soc. Rev. 2010, 39, 1600–1632. 2 2aN. Yoshikawa, Y. M. A. Yamada, J. Das, H. Sasai, M. Shibasaki, J. Am. Chem. Soc. 1999, 121, 4168–4178; 2bN. Yoshikawa, N. Kumagai, S. Matsunaga, G. Moll, T. Ohshima, T. Suzuki, M. Shibasaki, J. 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