LDA Conjugate Addition to a Morita-Baylis-Hillman Ester: Experimental and DFT-based Theoretical Observations

LDA Conjugate Addition to a Morita-Baylis-Hillman Ester: Experimental and DFT-based Theoretical Observations

Sousa, Bruno A.; Paulino, Antonio A. S.; Braga, Ataualpa A. C.; Ando, Romulo A.; Santos, Alcindo A. Dos

Abstract:

The Morita-Baylis-Hillman (MBH) reaction is well known for providing valuable building blocks in organic synthesis. In the last few years it has been demonstrated that not only the MBH adducts itself can be useful intermediates, but also, its derivatives. The corresponding esters of MBH adducts (acetates, in most cases) have been extensively described in the literature due to its particular reactivity towards the attack of different nucleophiles (Scheme 1). Scheme 1. The reactivity of MBH acetates towards the attack of different nucleophiles. the use of lithium amides is a very frequent strategy for synthetic chemists in order to produce reactive anionic intermediates. In the case of a MBH ester, the usual chemistry of lithium amides may not be absolute as already observed in different situations2. Herein we present an example of LDA conjugate addition to a MBH ester, also providing a Density Functional Theory (DFT)-based description of the reaction pathway, supporting the experimental unexpected results.

The Morita-Baylis-Hillman (MBH) reaction is well known for providing valuable building blocks in organic synthesis. In the last few years it has been demonstrated that not only the MBH adducts itself can be useful intermediates, but also, its derivatives. The corresponding esters of MBH adducts (acetates, in most cases) have been extensively described in the literature due to its particular reactivity towards the attack of different nucleophiles (Scheme 1). Scheme 1. The reactivity of MBH acetates towards the attack of different nucleophiles. the use of lithium amides is a very frequent strategy for synthetic chemists in order to produce reactive anionic intermediates. In the case of a MBH ester, the usual chemistry of lithium amides may not be absolute as already observed in different situations2. Herein we present an example of LDA conjugate addition to a MBH ester, also providing a Density Functional Theory (DFT)-based description of the reaction pathway, supporting the experimental unexpected results.

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DOI: 10.5151/chempro-15bmos-BMOS2013_201391621754

Referências bibliográficas

• [1] 1 Basavaiah, D.; Reddy, B. S.; Badsara, S. S. Chem. Rev. 2010, 110, 5447.
• [2] 2 Ma, Y.; Hoepker, A. C.; Gupta, L.; Faggin, M. F.; Collum, D. B. J. Am. Chem. Soc. 2010, 132, 15610.

Como citar:

Sousa, Bruno A.; Paulino, Antonio A. S.; Braga, Ataualpa A. C.; Ando, Romulo A.; Santos, Alcindo A. Dos; "LDA Conjugate Addition to a Morita-Baylis-Hillman Ester: Experimental and DFT-based Theoretical Observations", p-102-102. In: In Blucher Chemistry Proceedings, São Paulo, v. 1, n. 2, Dezembro.2013. São Paulo: Blucher, 2013.
ISSN 23184043, DOI 10.5151/chempro-15bmos-BMOS2013_201391621754