Modular access to chiral cyclopentanes via formal [2+2+1] annulation enabled by palladium/chiral squaramide relay catalysis

Lian-Feng Fan; Rui Liu; Pu-Sheng Wang; Liu-Zhu Gong

Tetrahedron Chem (Mar 2022)

Modular access to chiral cyclopentanes via formal [2+2+1] annulation enabled by palladium/chiral squaramide relay catalysis

Lian-Feng Fan,
Rui Liu,
Pu-Sheng Wang,
Liu-Zhu Gong

Affiliations

Lian-Feng Fan: Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China
Rui Liu: Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China
Pu-Sheng Wang: Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China; Corresponding author.
Liu-Zhu Gong: Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China; Center for Excellence in Molecular Synthesis of Chinese Academy of Sciences, Hefei, 230026, China; Corresponding author. Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China.

Journal volume & issue: Vol. 1
p. 100002

Abstract

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An enantio- and diastereodivergent [2+2+1] annulation reaction of allyl ketones, acidic methylene compounds, and nitroalkenes to assemble highly functionalized cyclopentanes from readily available substances enabled by asymmetric relay catalysis of chiral bifunctional squaramide and palladium complex has been established. This method showcases that allyl ketones can serve as latent 1,2-dication synthons via a linear-selective allylic C–H functionalization and sequential 1,4-conjugated addition, enabling the rapid assembly of cyclopentane skeleton with a broad scope of methylene nucleophiles and nitroalkenes. Notably, chiral bifunctional squaramide catalyst engages in both the intermolecular and intramolecular Michael addition reactions accompanying with a kinetic resolution behavior to amplify the enantioselection. In addition, the stereodivergent synthesis of diastereomers from the resultant chiral cyclopentane derivatives is also accessible by a simple manipulation with base.

Published in Tetrahedron Chem

ISSN: 2666-951X (Online)
Publisher: Elsevier
Country of publisher: United Kingdom
LCC subjects: Science: Chemistry: Organic chemistry
Website: https://www.journals.elsevier.com/tetrahedron-chem

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