Unique Divergent Reactivity of Boc-Protected Homopropargylic Alkoxyalkylamines in the Gold(I)-Catalyzed Domino Catalytic Reactions: Application to the Formal Synthesis of (–)-Pseudodistomin B

Ji Hyung Lee; Wook Jeong; Young Ho Rhee

doi:10.1055/s-0033-1338639

Synthesis, Table of Contents

Synthesis 2014; 46(16): 2155-2160
DOI: 10.1055/s-0033-1338639

special topic

Unique Divergent Reactivity of Boc-Protected Homopropargylic Alkoxyalkylamines in the Gold(I)-Catalyzed Domino Catalytic Reactions: Application to the Formal Synthesis of (–)-Pseudodistomin B

Ji Hyung Lee

Department of Chemistry, Pohang University of Science and Technology, Hyoja-dong san 31, Nam-gu, Pohang, Kyungbook 790-784, Republic of Korea Fax: +82(54)2793399 Email: yhrhee@postech.ac.kr

,

Wook Jeong

Department of Chemistry, Pohang University of Science and Technology, Hyoja-dong san 31, Nam-gu, Pohang, Kyungbook 790-784, Republic of Korea Fax: +82(54)2793399 Email: yhrhee@postech.ac.kr

,

Young Ho Rhee*

Department of Chemistry, Pohang University of Science and Technology, Hyoja-dong san 31, Nam-gu, Pohang, Kyungbook 790-784, Republic of Korea Fax: +82(54)2793399 Email: yhrhee@postech.ac.kr

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Abstract

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Abstract

By using t-Boc-protected homopropargylic alkoxyalkylamines as substrates, the reactivity between the carboxylation-promoted and the alkoxylation-promoted domino processes in the gold-catalyzed reaction was systematically compared. Interestingly, the result varies significantly depending upon the structure of the alkynes and the nature of the phosphine ligands. The alkoxylation-induced pathway represents a new synthetic method towards 2,4,5-trisubstituted piperidines. A formal synthesis of (–)-pseudodistomin B based upon this interesting chemoselectivity was accomplished.

Key words

gold catalysis - cyclization - piperidines - ligands - total synthesis

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References

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