[2,3]-Wittig Rearrangement as a Formal Asymmetric Alkylation of α-Branched Ketones

Mariliis Kimm; Maksim Ošeka; Sandra Kaabel; Andrus Metsala; Ivar Järving; Tõnis Kanger

doi:10.1021/acs.orglett.9b01495

[2,3]-Wittig Rearrangement as a Formal Asymmetric Alkylation of α-Branched Ketones

Mariliis Kimm, Maksim Ošeka, Sandra Kaabel, Andrus Metsala, Ivar Järving, Tõnis Kanger^*

^*Corresponding author for this work

Not published at Aalto University

Tallinn University of Technology

Research output: Contribution to journal › Article › Scientific › peer-review

10 Citations (Scopus)

Abstract

The enantioselective [2,3]-Wittig rearrangement of cinnamyloxycyclopentanone derivatives was performed in the presence of a Cinchona-based primary amine. The described method provides synthetically valuable α-hydroxy ketones with quaternary stereogenic centers in excellent enantiomeric purities. Relying on the X-ray crystal structure of the product and the DFT calculations, we propose that the rearrangement is promoted by an intramolecular hydrogen bond between the substrate and the catalyst.

Original language	English
Pages (from-to)	4976-4980
Number of pages	5
Journal	Organic Letters
Volume	21
Issue number	13
DOIs	https://doi.org/10.1021/acs.orglett.9b01495
Publication status	Published - 5 Jul 2019
MoE publication type	A1 Journal article-refereed

Funding

The authors thank the Estonian Ministry of Education and Research (Grant Nos. IUT 19-32, IUT19-9, PUT 692, and PUT 1468) and the Centre of Excellence in Molecular Cell Engineering (2014-2020.4.01.15-0013) for financial support. Authors thank Dr. Jasper Adamson (NICP, Tallinn, Estonia) for his assistance in NMR studies.

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10.1021/acs.orglett.9b01495

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abstract = "The enantioselective [2,3]-Wittig rearrangement of cinnamyloxycyclopentanone derivatives was performed in the presence of a Cinchona-based primary amine. The described method provides synthetically valuable α-hydroxy ketones with quaternary stereogenic centers in excellent enantiomeric purities. Relying on the X-ray crystal structure of the product and the DFT calculations, we propose that the rearrangement is promoted by an intramolecular hydrogen bond between the substrate and the catalyst.",

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AU - Kimm, Mariliis

AU - Ošeka, Maksim

AU - Kaabel, Sandra

AU - Metsala, Andrus

AU - Järving, Ivar

AU - Kanger, Tõnis

PY - 2019/7/5

Y1 - 2019/7/5

N2 - The enantioselective [2,3]-Wittig rearrangement of cinnamyloxycyclopentanone derivatives was performed in the presence of a Cinchona-based primary amine. The described method provides synthetically valuable α-hydroxy ketones with quaternary stereogenic centers in excellent enantiomeric purities. Relying on the X-ray crystal structure of the product and the DFT calculations, we propose that the rearrangement is promoted by an intramolecular hydrogen bond between the substrate and the catalyst.

AB - The enantioselective [2,3]-Wittig rearrangement of cinnamyloxycyclopentanone derivatives was performed in the presence of a Cinchona-based primary amine. The described method provides synthetically valuable α-hydroxy ketones with quaternary stereogenic centers in excellent enantiomeric purities. Relying on the X-ray crystal structure of the product and the DFT calculations, we propose that the rearrangement is promoted by an intramolecular hydrogen bond between the substrate and the catalyst.

UR - https://www.scopus.com/pages/publications/85068002193

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JO - Organic Letters

JF - Organic Letters

IS - 13

ER -

[2,3]-Wittig Rearrangement as a Formal Asymmetric Alkylation of α-Branched Ketones

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