The Trajectory of the (η5-Cyclopentadienyl)cobalt-Mediated Cycloisomerization of Ene-Yne-Ene-Type Allyl Propargylic Ethers to Furans: A DFT Appraisal

Jonathan J. Wong; Xiangyang Chen; Kendall N. Houk; K. Peter C. Vollhardt

doi:10.1055/a-1645-2632

Synlett, Inhaltsverzeichnis

Synthesis 2021; 53(22): 4279-4289
DOI: 10.1055/a-1645-2632

special topic

Special Issue dedicated to Prof. Sarah Reisman, recipient of the 2019 Dr. Margaret Faul Women in Chemistry Award

The Trajectory of the (η ⁵-Cyclopentadienyl)cobalt-Mediated Cycloisomerization of Ene-Yne-Ene-Type Allyl Propargylic Ethers to Furans: A DFT Appraisal

Jonathan J. Wong

^aDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, USA

,

Xiangyang Chen

^aDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, USA

,

Kendall N. Houk ∗

^aDepartment of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, USA

,

K. Peter C. Vollhardt ∗

^bDepartment of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460, USA

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Congratulations to Professor Sarah Reisman at the California Institute of Technology for having been chosen as the first recipient of the Dr. Margaret Faul Award for Women in Chemistry

Abstract

The mechanisms by which the complexes CpCoL₂ (Cp = C₅H₅; L = CO or CH₂=CH₂) mediate the cycloisomerizations of α,δ,ω-enynenes containing allylic ether linkages are probed by DFT methods. The outcomes corroborate experimental results and provide energetic and structural details of the trajectories leading to 3-(oxacyclopentyl or cycloalkyl)furans via the intermediacy of isolable CpCo-η ⁴-dienes. They comprise initial stereoselective complexation of one of the double bonds and the triple bond, rate-determining oxidative coupling to a triplet 16e cobalta-2-cyclopentene, and terminal double bond docking, followed by stereocontrolled insertion to assemble intermediate cis- and trans-fused triplet cobalta-4-cycloheptenes. A common indicator of the energetic facility of the latter is the extent of parallel alignment of the alkene moiety and its target Co–Cα bond. The cobalta-4-cycloheptenes transform further by β-hydride elimination–reductive elimination to furnish CpCo-η ⁴-dienes, which are sufficiently kinetically protected to allow for their experimental observation. The cascade continues through cobalt-mediated hydride shifts and dissociation of the aromatic furan ring. The findings in silico with respect to the stereo-, regio-, and chemoselectivity are in consonance with those obtained in vitro.

Key words

DFT - enynes - β-hydride elimination - cobalt - cycloisomerization - furans

Volltext

Referenzen

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Zusatzmaterial

The Trajectory of the (η 5-Cyclopentadienyl)cobalt-Mediated Cycloisomerization of Ene-Yne-Ene-Type Allyl Propargylic Ethers to Furans: A DFT Appraisal

The Trajectory of the (η ⁵-Cyclopentadienyl)cobalt-Mediated Cycloisomerization of Ene-Yne-Ene-Type Allyl Propargylic Ethers to Furans: A DFT Appraisal