Abstract
This protocol describes a new approach for the preparation of α-allylated α,β-unsaturated carbonyl compound by chemoselective cross-coupling of propargyl alcohols with allyl carbonates using an unprecedented vanadium/palladium contemporaneous dual catalysis. This process involves 1,3-transposition of propargyl alcohols by an oxyvanadium catalyst to generate vanadium allenoates and the activation of allyl carbonates by a palladium catalyst to generate π-allylpalladium species. These two active intermediates trap each other more rapidly to afford the observed product, rather than being intercepted by the large excess of starting propargyl alcohol. One example for the preparation of this type of α-allylated α,β-unsaturated carbonyl compound is included in the text. It takes ∼20 h to complete the protocol: 1.0 h to set up the reaction, 16 h for the reaction and 2.0 h for isolation and purification. This chemistry has been applied to obtain a wide range of α-allylated α,β-unsaturated ketones, esters and amides, which are highly valuable building blocks in organic synthesis.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Carey, F.A. & Sundberg, R.J. Advanced Organic Chemistry (Springer, New York, USA, 2007).
Trost, B.M. & Fleming, I. Comprehensive Organic Synthesis (Pergamon, Oxford, UK, 1991).
Wittig, G. & Schöllkopf, U. Über Triphenyl-phosphin-methylene als olefinbildende Reagenzien. Chem. Ber. 87, 1318–1330 (1954).
Mali, R.S. & Babu, K.N. Efficient synthesis of α-benyliden-γ-methyl-γ-butyrolactones. Helv. Chem. Acta 85, 3525–3531 (2002).
Peterson, D.J. Carbonyl olefination reaction using silyl-substituted organometallic compounds. J. Org. Chem. 33, 780–784 (1968).
Carcenac, Y. α- and β-Stannyl trifluoromethylbutenoates: regioselective preparation and use in copper(I)-catalyzed allylation and propargylation reactions. Adv. Synth. Catal. 352, 949–954 (2010).
Khamri, S., Turki, T. & Amri, H. Stereoselective synthesis of functionalized 1,4-dienes. Synth. Commun. 38, 3277–3284 (2008).
Kantam, M.L., Kumar, K.B.S. & Sreedhar, B. Rhodium fluorapatite catalyst for the synthesis of trisubstituted olefins via cross coupling of Baylis-Hillman adducts and arylboronic acids. J. Org. Chem. 73, 320–322 (2008).
Gendrineau, T., Demoulin, N., Navarre, L., Genet, J.P. & Darses, S. Rhodium-catalyzed formation of stereocontrolled trisubstituted alkenes from Baylis-Hillman adducts. Chem. Eur. J. 15, 4710–4715 (2009).
Park, J., Kwon, Y.B., Yang, K., Rhee, H. & Yoon, C.M. Efficient palladium-catalyzed coupling of Baylis-Hillman acetates with an allylstannane. Synthesis 4, 661–665 (2010).
Trost, B.M. & Oi, S. Atom economy: aldol-type products by vanadium-catalyzed additions of propargyl alcohols and aldehydes. J. Am. Chem. Soc. 123, 1230–1231 (2001).
Trost, B.M. & Luan, X. Contemporaneous dual catalysis by coupling highly transient nucleophilic and electrophilic intermediates generated in situ. J. Am. Chem. Soc. 133, 1706–1709 (2011).
Trost, B.M., Luan, X. & Miller, Y. Contemporaneous dual catalysis: chemoselective cross-coupling of catalytic vanadium-allenoate and π-allylpalladium intermediates. J. Am. Chem. Soc. 133, 12824–12833 (2011).
Trost, B.M. & Jonasson, C. Vanadium-catalyzed anti-selective additions of allenols to imines. Angew. Chem. Int. Ed. 42, 2063–2066 (2003).
Shintani, R., Okamoto, K. & Hayashi, T. Rhodium-catalyzed isomerization of α-arylpropargyl alcohols to indanones: involvement of an unexpected reaction cascade. J. Am. Chem. Soc. 127, 2872–2873 (2005).
Tsuji, J., Sato, K. & Okumoto, H. Palladium-catalyzed decarboxylation-carbonylation of allylic carbonates to form β,γ-unsaturated esters. J. Org. Chem. 49, 1341–1344 (1984).
Still, W.C., Kahn, M. & Mitra, A. A rapid chromatographic method. J. Org. Chem. 43, 2923–2925 (1978).
Acknowledgements
We thank the US National Science Foundation (CHE 0948222) for financial support of this project. X.L. is grateful for a Swiss National Science Foundation postdoctoral fellowship.
Author information
Authors and Affiliations
Contributions
X.L. carried out experimental procedure development, synthetic work and assembly of the manuscript collaboratively with and under the supervision of B.M.T.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Rights and permissions
About this article
Cite this article
Trost, B., Luan, X. Synthesis of α-allylated α,β-unsaturated carbonyl compounds using vanadium/palladium contemporaneous dual catalysis. Nat Protoc 7, 1497–1501 (2012). https://doi.org/10.1038/nprot.2012.076
Published:
Issue Date:
DOI: https://doi.org/10.1038/nprot.2012.076
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
