Direct Enantio‐ and Diastereoselective Oxidative Homo‐Coupling of Aldehydes

Line Næsborg; Lars Leth; Gabriel Jose Reyes Rodriguez; Teresa Ann Palazzo; Karl Anker Jørgensen

doi:10.1002/chem.201803506

Direct Enantio‐ and Diastereoselective Oxidative Homo‐Coupling of Aldehydes

Line Næsborg, Lars Leth, Gabriel Jose Reyes Rodriguez, Teresa Ann Palazzo, Karl Anker Jørgensen

Department of Chemistry

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

Abstract

A novel strategy for the direct enantioselective oxidative homocoupling of α-branched aldehydes is presented. The methodology employs open-shell intermediates for the construction of chiral 1,4-dialdehydes by forming a carbon–carbon bond connecting two quaternary stereogenic centers in good yields and excellent stereoselectivities for electron-rich aromatic aldehydes. The 1,4-dialdehydes were transformed into synthetically valuable chiral pyrrolidines. Experimental mechanistic investigations based on competition experiments combined with computational studies indicate that the reaction proceeds through a radical cation intermediate and that reactivity and stereoselectivity follow different trends.

Original language	English
Journal	Chemistry: A European Journal
Volume	24
Issue	55
Pages (from-to)	14844-14848
Number of pages	5
ISSN	0947-6539
DOIs	https://doi.org/10.1002/chem.201803506
Publication status	Published - 10 Jul 2018

Keywords

Hammett analysis
density functional calculations
organocatalysis
oxidative coupling of aldehydes
pyrrolidines

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10.1002/chem.201803506

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title = "Direct Enantio‐ and Diastereoselective Oxidative Homo‐Coupling of Aldehydes",

abstract = "A novel strategy for the direct enantioselective oxidative homocoupling of α-branched aldehydes is presented. The methodology employs open-shell intermediates for the construction of chiral 1,4-dialdehydes by forming a carbon–carbon bond connecting two quaternary stereogenic centers in good yields and excellent stereoselectivities for electron-rich aromatic aldehydes. The 1,4-dialdehydes were transformed into synthetically valuable chiral pyrrolidines. Experimental mechanistic investigations based on competition experiments combined with computational studies indicate that the reaction proceeds through a radical cation intermediate and that reactivity and stereoselectivity follow different trends.",

keywords = "Hammett analysis, density functional calculations, organocatalysis, oxidative coupling of aldehydes, pyrrolidines",

author = "Line N{\ae}sborg and Lars Leth and {Reyes Rodriguez}, {Gabriel Jose} and Palazzo, {Teresa Ann} and J{\o}rgensen, {Karl Anker}",

year = "2018",

month = jul,

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doi = "10.1002/chem.201803506",

language = "English",

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Direct Enantio‐ and Diastereoselective Oxidative Homo‐Coupling of Aldehydes. / Næsborg, Line; Leth, Lars; Reyes Rodriguez, Gabriel Jose et al.
In: Chemistry: A European Journal, Vol. 24, No. 55, 10.07.2018, p. 14844-14848.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - Direct Enantio‐ and Diastereoselective Oxidative Homo‐Coupling of Aldehydes

AU - Næsborg, Line

AU - Leth, Lars

AU - Reyes Rodriguez, Gabriel Jose

AU - Palazzo, Teresa Ann

AU - Jørgensen, Karl Anker

PY - 2018/7/10

Y1 - 2018/7/10

N2 - A novel strategy for the direct enantioselective oxidative homocoupling of α-branched aldehydes is presented. The methodology employs open-shell intermediates for the construction of chiral 1,4-dialdehydes by forming a carbon–carbon bond connecting two quaternary stereogenic centers in good yields and excellent stereoselectivities for electron-rich aromatic aldehydes. The 1,4-dialdehydes were transformed into synthetically valuable chiral pyrrolidines. Experimental mechanistic investigations based on competition experiments combined with computational studies indicate that the reaction proceeds through a radical cation intermediate and that reactivity and stereoselectivity follow different trends.

AB - A novel strategy for the direct enantioselective oxidative homocoupling of α-branched aldehydes is presented. The methodology employs open-shell intermediates for the construction of chiral 1,4-dialdehydes by forming a carbon–carbon bond connecting two quaternary stereogenic centers in good yields and excellent stereoselectivities for electron-rich aromatic aldehydes. The 1,4-dialdehydes were transformed into synthetically valuable chiral pyrrolidines. Experimental mechanistic investigations based on competition experiments combined with computational studies indicate that the reaction proceeds through a radical cation intermediate and that reactivity and stereoselectivity follow different trends.

KW - Hammett analysis

KW - density functional calculations

KW - organocatalysis

KW - oxidative coupling of aldehydes

KW - pyrrolidines

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U2 - 10.1002/chem.201803506

DO - 10.1002/chem.201803506

M3 - Journal article

C2 - 29992673

SN - 0947-6539

VL - 24

SP - 14844

EP - 14848

JO - Chemistry: A European Journal

JF - Chemistry: A European Journal

IS - 55

ER -

Direct Enantio‐ and Diastereoselective Oxidative Homo‐Coupling of Aldehydes

Abstract

Keywords

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