Organocatalytic Asymmetric 1,6‐Addition Reactions

Biju, Akkattu T.

doi:10.1002/cctc.201100279

Cited by 78 publications

(8 citation statements)

References 80 publications

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“…[1,2] Recently the field of organocatalysis has been developing rapidly [3] and organocatalysts have been successfully employed in the asymmetric, catalytic Michael reaction, in which most of the reactions are those of a,b-unsaturated electron withdrawing group. [4] As for the organocatalyst-mediated asymmetric 1,4-and 1,6-addition reactions, [5] Jørgensen and coworkers reported the selective 1,6-addition reaction of a,b-g,d-diunsaturated ketones with b-keto ester and benzophenone imine using cinchona alkaloids under phase transfer conditions. [6] Although the same nucleophile was employed, a chiral enamine derived from aldehyde and diphenylprolinol silyl ether, [7] the 1,6-addition proceeds between aldehyde to dienic sulfones, [8] whereas the 1,4-addition occurs between aldehyde and nitrodiene, [9] both of which are reported by Alexakis and coworkers.…”

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confidence: 99%

Organocatalytic 1,4‐Addition Reaction of α,β‐γ,δ‐Diunsaturated Aldehydes versus 1,6‐Addition Reaction

et al. 2012

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Michael reaction of carbon nucleophile is one of the most important carbon-carbon bond forming reactions in organic synthesis. [1] In the nucleophilic addition to a,b-g,d-diunsaturated carbonyl compounds, there are three possible reaction paths such as 1,2-, 1,4-, and 1,6-addition reactions. As for the asymmetric catalytic method, there are several successful selective 1,4-and 1,6-addition reactions catalyzed by transition-metal catalysts. [1,2] Recently the field of organocatalysis has been developing rapidly [3] and organocatalysts have been successfully employed in the asymmetric, catalytic Michael reaction, in which most of the reactions are those of a,b-unsaturated electron withdrawing group. [4] As for the organocatalyst-mediated asymmetric 1,4-and 1,6-addition reactions, [5] Jørgensen and coworkers reported the selective 1,6-addition reaction of a,b-g,d-diunsaturated ketones with b-keto ester and benzophenone imine using cinchona alkaloids under phase transfer conditions. [6] Although the same nucleophile was employed, a chiral enamine derived from aldehyde and diphenylprolinol silyl ether, [7] the 1,6-addition proceeds between aldehyde to dienic sulfones, [8] whereas the 1,4-addition occurs between aldehyde and nitrodiene, [9] both of which are reported by Alexakis and coworkers. Ma reported 1,4-addition of dibenzyl malonate and a,b-g,ddiunsaturated aldehyde catalyzed by diphenylprolinol silyl [**]

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Organocatalytic 1,4‐Addition Reaction of α,β‐γ,δ‐Diunsaturated Aldehydes versus 1,6‐Addition Reaction

et al. 2012

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“…In conjunction with our study on the development of chiral P -spiro iminophosphorane-catalysed regio-, diastereo- and enantioselective conjugate addition reactions, we herein report a complete inversion of diastereoselectivity in the 1,6-addition333435363738394041424344 of azlactones (oxazol-5(4 H )-ones) to δ-aryl dienyl carbonyl compounds enabled by the slight structural alteration of iminophosphorane catalyst 1 (Fig. 1)374546474849.…”

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confidence: 68%

Complete diastereodivergence in asymmetric 1,6-addition reactions enabled by minimal modification of a chiral catalyst

Uraguchi¹,

Yoshioka²,

Ooi³

2017

Nat Commun

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Catalytic systems that allow selective generation of any diastereomer of a reaction product bearing multiple stereocentres through minimal modification of a single catalyst scaffold remain elusive, particularly for carbon–carbon bond formations requiring simultaneous control of multiple selectivity factors. Here, we report a catalyst-directed pinpoint inversion of diastereochemical preference in the 1,6-addition of azlactones to δ-aryl dienyl carbonyl compounds with full control over other selectivities preserved. This rigorous diastereodivergence is enabled by the slight structural adjustment of a chiral iminophosphorane catalyst, providing access to all the stereoisomers with high regio-, distereo- and enantioselectivity. The utility of this method is demonstrated in the facile stereodivergent preparation of densely functionalized proline derivatives. The experimental and computational elucidation of the origin of the diastereodivergence is also reported.

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“…For reviews of organocatalyzed conjugate additions see reference [53] (1,4-addition) and reference [54] (1,6-addition). 1,3-Dicarbonyl compounds are famous nucleophiles in Michael reactions for the demonstration of a new catalyst's potential due to their high reactivity.…”

Section: Conjugate Additionsmentioning

confidence: 99%

Recent Advances in Organocatalytic Methods for Asymmetric CC Bond Formation

Scheffler

Mahrwald

2013

Chemistry A European J

200

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Beyond a doubt organocatalysis belongs to the most exciting and innovative chapters of organic chemistry today. Organocatalysis has emerged not only as a complement to metal-catalyzed reactions and to biocatalysis over the last decade, but also provides new asymmetric organocatalyzed reactions that cannot be accomplished by metal- or biocatalyzed reactions so far. A large number of organocatalytic processes are already well established in organic synthesis. Nevertheless, the number of publications in this field is still on the increase; new important results are produced constantly. This review gives a detailed overview of the latest developments and main streams in organocatalyzed asymmetric CC bond formation processes of the last three years. It is intended to outline the most important current findings focused on especially new synthetic methodologies.

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Organocatalytic Asymmetric 1,6‐Addition Reactions

Cited by 78 publications

References 80 publications

Organocatalytic 1,4‐Addition Reaction of α,β‐γ,δ‐Diunsaturated Aldehydes versus 1,6‐Addition Reaction

Organocatalytic 1,4‐Addition Reaction of α,β‐γ,δ‐Diunsaturated Aldehydes versus 1,6‐Addition Reaction

Complete diastereodivergence in asymmetric 1,6-addition reactions enabled by minimal modification of a chiral catalyst

Recent Advances in Organocatalytic Methods for Asymmetric CC Bond Formation

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