An Efficient Synthesis of an Apoptosis Inducer, F-3-2-5 by Using Octanol-Accelerated Baylis-Hillman Reaction

Kang, Seock-Yong; Park, Kwang‐Su; Kim, Jin‐Young; Chong, Youhoon; Choo, Hyunah

doi:10.5012/bkcs.2007.28.2.179

Cited by 4 publications

References 17 publications

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Baylis‐Hillman Reaction

2010

Comprehensive Organic Name Reactions and Reagents

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The Baylis‐Hillman reaction is a three‐component reaction involving the coupling of the α‐position of activated alkenes with carbon electrophiles (i.e., aldehydes) under the influence of a catalyst/catalyst system, with the characteristics of atom efficiency and the formation of dense functionality. Similarly, the corresponding reaction between alkenes and imines under same conditions is referred to as the aza‐Baylis‐Hillman reaction or aza‐Morita‐Baylis‐Hillman reaction. Some of the cases, this reaction is also cited as Morita reaction, Morita‐Baylis‐Hillman alkylation, and Morita‐Baylis‐Hillman cyclization. In this reaction, the activated alkenes include acrylonitrile, acrolein, acrylates, and α,β‐unsaturated ketones. Various types of the catalyst system have been applied in this reaction. Some shortcomings of the reaction have been reported, such as the slow reaction rate, being limited to electrophilic α,β‐unsaturated carbonyl compounds, and almost exclusively occuring in the reactions involving β‐unsubstituted α,β‐unsaturated carbonyl compounds and cyclic enones. Therefore, different measures have been taken to optimize this reaction.

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Baylis‐Hillman Reaction

2010

Comprehensive Organic Name Reactions and Reagents

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A computational study of the Hofmann elimination pathway for Morita–Baylis–Hillman reaction under DABCO catalysis: Participation of a bridge‐head ylide

Yadav

2021

J of Physical Organic Chem

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In comparison to the popular pathway involving proton-transfer via a four-centred cyclic transition state structure, the recently proposed overall lower energy pathway involving proton-transfer via a seven-centred cyclic transition state structure followed by Hofmann elimination for the Me 3 N-catalyzed Morita-Baylis-Hillman reaction is applicable to the DABCO-catalyzed reaction equally well. This finding clearly establishes that the zwitterion at the bridge-head in DABCO is well tolerated. Also, the activation free energy of the rate-limiting aldol reaction under DABCO-catalysis is lower than that under Me 3 N-catalysis, suggesting that DABCO is likely a better catalyst to achieve faster conversion. File list (2) download file view on ChemRxiv manuscript-13042020.pdf (793.15 KiB) download file view on ChemRxiv SI-13042020.pdf (536.08 KiB) A computational study of the Hofmann elimination pathway for the Morita-Baylis-Hillman reaction under DABCO catalysis. Participation of a bridge-head ylide

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