An Efficient Synthesis of Thiophene/Pyrrole-Fused Crown Ethers Using Mitsunobu Reaction for Potential Application to Sensory Electroactive Polymers

Kim, Joongchul; Yoon, Daehyun; Lee, Sangeun; Ko, Seokbeom; Lee, Youn-Sik; Zong, Kyukwan

doi:10.5012/bkcs.2006.27.11.1910

Cited by 5 publications

(1 citation statement)

References 11 publications

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“…Alcohols are converted into esters, ethers, amines, amides, and related derivatives . Due to this advantage, Mitsunobu reactions have been widely applied not only in the field of small molecule synthesis , but also in the field of bioorganic chemistry, such as structural modifications of saccharides, peptides, and nucleic acids, and also in polymer synthesis . However, a major drawback of conventional Mitsunobu reactions is that stoichiometric amounts of the azodicarboxylate and phosphine reagents must be used, and the hydrazine and phosphine oxide side products are not easily separated from the crude product mixtures (Figure A), although various methods have been developed to address this issue .…”

Section: Introductionmentioning

confidence: 99%

Computational Exploration of a Redox-Neutral Organocatalytic Mitsunobu Reaction

2020

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The mechanism of the redox-neutral organocatalytic Mitsunobu reaction, catalyzed by (2-hydroxybenzyl)diphenylphosphine oxide, reported by Denton et al., has been studied computationally with ωB97X-D density functional theory. We discovered that the nucleophilic substitution reaction between carboxylate and alkoxyphosphonium ions, to reform the phosphine oxide catalyst, is the rate-determining step of the overall process and is significantly accelerated compared with a general-acid-catalyzed SN2 reaction. The (2-hydroxybenzyl)diphenylphosphine oxide is regenerated and activated in every catalytic cycle via intramolecular dehydration/cyclization. We also designed several phosphine oxide catalysts that we predict to be more effective catalysts.

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