MnO2 mediated sequential oxidation/olefination of alkyl-substituted heteroarenes with alcohols

doi:10.1016/j.tet.2020.130968

Tetrahedron

Volume 76, Issue 11, 13 March 2020, 130968

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Abstract

A practical and efficient ligand-free MnO₂ mediated sequential oxidation and olefination has been developed for the facile synthesis of a broad range of unsaturated N-heteroazaarenes from simple alkyl-substituted heteroarenes and alcohols. The procedure tolerates a series of functional groups, such as methoxyl, chloro, bromo, iodo, vinyl, phenolic and hetero groups, providing the olefination products in moderate to good yields.The protocol could be conducted at mild conditions and used environmentally friendly air as the clear oxidant.

Graphical abstract

Introduction

As one of the most important fundamental structural motifs, unsaturated N-heteroaromatic compounds has been considered as a privileged structure in natural products, pharmaceuticals and functional materials (Fig. 1).[1] As such, the development of efficient methods toward these complex molecules is of great significance to chemical, medicinal and material science and has attracted a great deal of attention over the past decades.[2] Plenty of powerful synthetic routes, including many named reactions,[3] catalytic coupling [4] or olefin metathesis, [5] have been developed to access such kinds of molecules. However, multi-step functional group manipulations and unavoidable generation of stoichiometric amount of undesired waste are the few shortcomings in these reactions.

An attractive approach to circumvent these problems is abundantly available metal catalyzed acceptorless dehydrogenative condensation (ADC),[6] which enables the synthesis of di-substituted alkenes compounds from alcohols combination of catalytic dehydrogenation and condensation steps. Moreover, alcohols can be obtained from indigestible and abundantly available lignocellulose biomass.[7] Kempe [8] and Maji group [9] pioneered a novel manganese-catalyzed reaction leading to di-substituted olefins synthesis using alcohols with N-heteroarenes at the same time, the reaction proceeds via ADC process producing only water and hydrogen as green coproducts (Scheme 1 top). However, metal complexes or addition of capricious ligands for catalyst activation are generally required to maintain the catalytic cycle, thereby limiting the potential scope of this environmentally benign transformation. These results together with our progress on the use of alcohols as green partners for metal catalyzed coupling reactions, [10] prompted us to envision that alcohols might be oxidized in MnO₂/air catalytic system and condensed with methylazaarenes for the synthesis of di-substituted olefins. Moreover, to the best of our knowledge, MnO₂ catalyzed oxidation/olefination of alcohols and methylazaarenes to synthesis unsaturated N-heteroaromatic has not been reported. Herein, we present on the first protocol for successful implementation of the MnO₂ catalyzed oxidation of alcohols with a variety of alkyl-substituted azaarenes via olefination process, which allows for synthesis of various multiple-substituted alkenes under mild condition Scheme 1.

Section snippets

Results and discussion

As an initial attempt, the reaction between phenylmethanol (1a) and 2-methylpyrazine (2a) was chosen as the model reaction for optimization of the reaction conditions (Table 1).

Because manganese precatalyst has shown to be highly effective for the dehydragenation/olefination of methylazaarenes with alcohols [8,9], we initially focused on exploring conditions using MnO₂ as readily available catalyst at 120 °C. The desired (E)-2-styrylpyrazine (3a) was obtained in 12% yield, when the reaction was

Conclusion

In summary, we have developed an efficient MnO₂/air catalytic system that allows the direct formation of unsaturated N-heteroaromatics from commercially available alcohols and alkylazaarenes via oxidation/olefination under the aerobic conditions. The method is compatible with a variety of functional groups and can be used to prepare a range of 1,2-disubstitued unsaturated N-heteroaromatics. Further investigations to gain a detailed mechanistic understanding as well as application of this

General information

¹H and ¹³C spectra were obtained on a Brüker AVIII300 (300 MHz) or AVII (500 MHz) spectrometer. Proton-decoupled spectra are denoted as {¹H}. Chemical shifts (δ) were reported in parts per million (ppm) using the residual solvent signal as an internal standard (CDCl₃: δ_H = 7.26 ppm, δ_C = 77.16 ppm). All coupling constants (J values) were reported in Hertz (Hz). Multiplicities were reported as follows: s, singlet; d, doublet; t, triplet; m, multiplet. High-resolution mass spectrometry (HRMS)

Notes

The authors declare no competing financial interest.

Acknowledgments

This research was supported by the Natural Science Foundation of Shandong Province (Nos. ZR2017MB029, ZR2017BB060),the Natural Science Foundation of Qingdao City (18-2-2-49-jch), the Open project of Chemistry Department of Qingdao University of Science and Technology (QUSTHX201921, QUSTHX202010) for financial support.

References (10)

(For selected examples,...M. Murakami et al.
J. Am. Chem. Soc.
(2003)
R. Dumeunier et al.L.-C. Campeau et al.
J. Am. Chem. Soc.
(2005)
J.-P. Leclerc et al.
Angew. Chem. Int. Ed.
(2006)
K.S. Kanyiva et al.
Angew. Chem. Int. Ed.
(2007)
L.-C. Campeau et al.
J. Am. Chem. Soc.
(2008)
L.-C. Campeau et al.
J. Am. Chem. Soc.
(2008)
A. Larivée et al.
J. Am. Chem. Soc.
(2008)
Y. Nakao et al.
J. Am. Chem. Soc.
(2008)
M. Tobisu et al.
J. Am. Chem. Soc.
(2009)
J. Wu et al.
J. Am. Chem. Soc.
(2009)
M. Kim et al.
Angew. Chem. Int. Ed.
(2009)
J.J. Mousseau et al.
Angew. Chem. Int. Ed.
(2010)
M. Hirano Fukumoto et al.
J. Org. Chem.
(2017)
T.-Y. Feng et al.
J. Org. Chem.
(2017)
F. Xiao et al.
J. Org. Chem.
(2018)
S.-S. Li et al.
Org. Lett.
(2018)
G. Zhang et al.
Angew. Chem. Int. Ed.
(2018)
M.K. Barman et al.
Angew. Chem. Int. Ed.
(2018)
S. Matar et al.G.D. Henry
Tetrahedron
(2004)
J.P. Michael
Nat. Prod. Rep.
(2005)
T. Laird
Org. Process Res. Dev.
(2006)
L.-C. Campeau et al.
Chem. Soc. Rev.
(2007)
M.C. Bagley et al.
Synlett
(2007)
S. Wang et al.
Chem. Commun.
(2008)
J.C. Jung et al.
Eur. J. Med. Chem.
(2009)
D. Simoni et al.
Bioorg. Med. Chem. Lett
(2006)
N.-Y. Kang et al.
Chem. Soc. Rev.
(2011)
Q. Li et al.
Angew. Chem. Int. Ed.
(2004)
R. Fanelli et al.
J. Med. Chem.
(2015)
S. Jiang et al.
Angew. Chem. Int. Ed.
(2017)
S. Jiang et al.
Angew. Chem. Int. Ed.
(2017)
(For selected examples of Witting reaction,...G. Wittig et al.
Justus Liebigs Ann. Chem.
(1953)
B.E. Maryanoff et al.
Chem. Rev.
(1989)
Q.-Q. Li et al.
J. Org. Chem.
(2018)
C. Schultze et al.
J. Org. Chem.
(2018)
L. Horner et al.
Chem. Ber.
(1959)
W.S. Wadsworth et al.
J. Am. Chem. Soc.
(1961)
J. Clayden et al.
Angew. Chem. Int. Ed.
(1996)
D.J. Peterson
J. Org. Chem.
(1968)
L.F.v. Staden et al.
Chem. Soc. Rev.
(2002)
M.C. Fernández et al.
J. Org. Chem.
(2006)
R.E. Beveridge et al.
Org. Lett.
(2013)
M. Julia et al.
Tetrahedron Lett.
(1973)
S. Banerjee et al.
J. Org. Chem.
(2016)
A.K. Simlandy et al.
J. Org. Chem.
(2017)

There are more references available in the full text version of this article.

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¹: These authors contributed equally to this work.

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MnO2 mediated sequential oxidation/olefination of alkyl-substituted heteroarenes with alcohols

Abstract

Graphical abstract

Introduction

Section snippets

Results and discussion

Conclusion

General information

Notes

Acknowledgments

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Angew. Chem. Int. Ed.

Angew. Chem. Int. Ed.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Angew. Chem. Int. Ed.

Angew. Chem. Int. Ed.

J. Org. Chem.

J. Org. Chem.

J. Org. Chem.

Org. Lett.

Angew. Chem. Int. Ed.

Angew. Chem. Int. Ed.

Tetrahedron

Nat. Prod. Rep.

Org. Process Res. Dev.

Chem. Soc. Rev.

Synlett

Chem. Commun.

Eur. J. Med. Chem.

Bioorg. Med. Chem. Lett

Chem. Soc. Rev.

Angew. Chem. Int. Ed.

J. Med. Chem.

Angew. Chem. Int. Ed.

Angew. Chem. Int. Ed.

Justus Liebigs Ann. Chem.

Chem. Rev.

J. Org. Chem.

J. Org. Chem.

Chem. Ber.

J. Am. Chem. Soc.

Angew. Chem. Int. Ed.

J. Org. Chem.

Chem. Soc. Rev.

J. Org. Chem.

Org. Lett.

Tetrahedron Lett.

J. Org. Chem.

J. Org. Chem.

MnO₂ mediated sequential oxidation/olefination of alkyl-substituted heteroarenes with alcohols