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Synfacts 2014; 10(3): 0269
DOI: 10.1055/s-0033-1340685
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Tandem Enantioselective Zinc-Promoted Reaction

Contributor(s):
Hisashi Yamamoto
,
Atsuto Izumiseki
Smirnov P, Mathew J, Nijs A, Katan E, Karni M, Bolm C, Apeloig Y, Marek I * Technion-Israel Institute of Technology, Haifa, Israel and RWTH Aachen University, Germany
One-Pot Zinc-Promoted Asymmetric Alkynylation/Brook-Type Rearrangement/Ene–Allene Cyclization: Highly Selective Formation of Three New Bonds and Two Stereocenters in Acyclic Systems.

Angew. Chem. Int. Ed. 2013;
52: 13717-13721
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Further Information

Publication History

Publication Date:
17 February 2014 (online)

 
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Key words

zinc - Brook rearrangement - alkynylation

Significance

In a one-pot operation, two stereocenters and three new bonds were created with high selectivity. The reaction proceeds through a sequence of asymmetric alkynylation of an acyl ­silane, tandem Brook-type rearrangement, ene–allene cyclization, addition of an electrophile, and finally oxidation. It will be extremely useful in organic synthesis, and it is a new approach to synthetic transformations.


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Comment

Quantum mechanical calculations show that this method passes through an allenyl Zn-Brook rearrangement and that this transformation bypasses the intermediate derived from the classic [1,2]-Brook rearrangement. This important finding nicely rationalizes the observation that the rearrangement proceeds without racemization.


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