Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2009 Feb 19;11(4):827-30.
doi: 10.1021/ol802828d.

Catalytic redox-initiated glycolate aldol additions of silyl glyoxylates

Stephen N Greszler  1 , Jeffrey S Johnson
Affiliations

Catalytic redox-initiated glycolate aldol additions of silyl glyoxylates

Stephen N Greszler et al. Org Lett. .

Abstract

Lanthanide triisopropoxides catalyze a rapid, tandem MPV reduction/Brook rearrangement/aldol sequence between silyl glyoxylates and aldehydes that achieves catalytic turnover through alkoxide transfer from a strain-release Lewis acidic silacycle.

PubMed Disclaimer

Figures

Figure 1
Figure 1
Catalytic Reductive Aldol Reaction - Proposal
Figure 2
Figure 2
Summary of Initial Catalyst and Turnover Reagent Screens
Figure 3
Figure 3
Possible Hydride Transfer Pathways
Figure 4
Figure 4
Isotopic Labeling Studya a Conditions: 1.5 equiv of PhCHO, 2 equiv of 10, [1]0 = 0.2 M.
Figure 5
Figure 5
Proposed Catalytic Cycle Employing Silacycle 6c
See this image and copyright information in PMC

References

    1. Linghu X, Satterfield AD, Johnson JS. J Am Chem Soc. 2006;128:9302–9303. - PMC - PubMed

    1. Kim IS, Ngai MY, Krische MJ. J Am Chem Soc. 2008;130:14891–14899.Kim IS, Ngai MY, Krische MJ. J Am Chem Soc. 2008;130:6340–6341.Catalytic functionalization of carbinol C-H bonds have also been achieved: Shi L, Tu Y-Q, Wang M, Zhang F-M, Fan C-A, Zhao Y-M, Xia W-J. J Am Chem Soc. 2005;127:10836–10837.

    1. Mahrwald R, editor. Modern Aldol Reactions. Wiley-VCH; Weinheim, Germany: 2004. For a monograph on the aldol reaction.

    1. For reduction of acyl silanes, see: Bolm C, Kasyan A, Heider P, Saladin S, Drauz K, Guenther K, Wagner C. Org Lett. 2002;4:2265–2267.Brook AG, Quigley MA, Peddle GJD, Schwartz NV, Warner CM. J Am Chem Soc. 1960;82:5102–5106.Reich HJ, Holtan RC, Bolm C. J Am Chem Soc. 1990;112:5609–5617.

    1. Kinnaird JWA, Ng PY, Kubota K, Wang X, Leighton JL. J Am Chem Soc. 2002;124:7920–7921. - PubMed
    2. Wang X, Meng Q, Perl NR, Yue X, Leighton JL. J Am Chem Soc. 2005;127:12806–12807. - PubMed
    3. Myers AG, Widdowson KL, Kukkola PJ. J Am Chem Soc. 1992;114:2765–2767.
    4. Denmark SE, Griedel BD, Coe DM. J Org Chem. 1993;58:988–990.
    5. Sunderhaus JD, Lam H, Dudley GB. Org Lett. 2003;5:4571–4573. - PubMed

Publication types