Stereoselective Synthesis of Polysubstituted Conjugated Dienes Enabled by Photo-Driven Sequential Sigmatropic Rearrangement.

Ji, Xin; Shen, Chaoren; Ni, Yuhao; Si, Zhi-Yao; Wang, Yuzhu; Zhi, Xinrong; Zhao, Yuting; Peng, Huiling; Liu, Lu

Ji, Xin; Shen, Chaoren; Ni, Yuhao; Si, Zhi-Yao; Wang, Yuzhu; Zhi, Xinrong; Zhao, Yuting; Peng, Huiling; Liu, Lu.

Afiliación

Ji X; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Shen C; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Ni Y; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Si ZY; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Wang Y; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Zhi X; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Zhao Y; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Peng H; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Liu L; School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.

Angew Chem Int Ed Engl ; 63(24): e202400805, 2024 Jun 10.

Article en En | MEDLINE | ID: mdl-38587996

ABSTRACT

ABSTRACT

We here reported a highly stereoselective method for the synthesis of polysubstituted conjugated dienes from α-aryl α-diazo alkynyl ketones and pyrazole-substituted unsymmetric aminals under mild conditions, which was promoted by photo-irridation and involved with 1,6-dipolar intermediate and quadruple sigmatropic rearrangements, was successfully developed. In this transformation, the cleavage of four bonds and the recombination of five bonds were implemented in one operational step. This protocol provided a modular tool for constructing dienes from amines, pyrazoles and α-alkynyl-α-diazoketones in one-pot manner. The results of mechanistic investigation indicated that the plausible reaction path underwent the 1,6-sigmatropic rearrangement instead of the 1,5-sigmatropic rearrangement.

Palabras clave

1,6-dipolar ion; Wolff rearrangement; conjugated diene; diazo compounds; sigmatropic rearrangement

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