A serendipitous Rauhut-Currier dimerization of 1,1-disubstituted activated olefins derived from Morita-Baylis-Hillman adducts was observed in the presence of DABCO. The reaction is driven by the migration of an acyl group and produces multifunctionalized enol esters in yields greater than 90% in most cases, without necessitating column chromatographic purification. The acyl transfer is thought to proceed via a transition state typical of a Morita-Baylis-Hillman (MBH) reaction, supported by a brief mechanistic study involving computational calculations.
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http://dx.doi.org/10.1021/acs.joc.2c02244 | DOI Listing |
Chem Sci
December 2024
Department of Chemistry, Korea Advanced Institute of Science & Technology (KAIST) Daejeon 34141 Republic of Korea
Securinega alkaloids, known for their unique structures and neuroplasticity-inducing potential, are promising candidates for treating neurodegenerative diseases such as depression and substance use disorders (SUD). Herein, we delineate the total synthesis of two dimeric Rauhut-Currier (RC) reaction-based securinega alkaloids, (-)-flueggenine A and (-)-15'--flueggenine D. The key step involved a novel reductive Heck dimerization strategy, utilizing a silyl-tethered enone coupling partner to ensure the desired reactivity and stereoselectivity.
View Article and Find Full Text PDFChem Asian J
November 2024
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, Dalian University of Technology, 2 Linggong Road, Dalian, 116024, China.
Herein, a facile head-to-tail dimerization of alkyl crotonates using electron-rich N,N'-bis(imidazolyl) guanidinylphosphines (BIG-Ps) as organocatalysts was firstly developed. This reaction proceeded smoothly under mild reaction conditions, effectively generating a series of functionalized 2-ethylidene-3-methylpentanedioates in excellent yields and stereoselectivity. Furthermore, this method was successfully applied for the synthesis of unsaturated polyesters by employing alkyl dicotonates as monomers.
View Article and Find Full Text PDFBeilstein J Org Chem
February 2023
Division of Organic Chemistry, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pune-411 008, India.
The total synthesis of racemic incarvilleatone has been achieved by utilizing unexplored accelerated Rauhut-Currier (RC) dimerization. The other key steps of the synthesis are oxa-Michael and aldol reactions in a tandem sequence. Racemic incarvilleatone was separated by chiral HPLC and the configuration of each enantiomer was determined by single-crystal X-ray analysis.
View Article and Find Full Text PDFJ Org Chem
February 2023
Department of Chemistry, School of Chemical Sciences and Pharmacy, Central University of Rajasthan, NH-8, Bandarsindri, Ajmer 305817, Rajasthan, India.
A serendipitous Rauhut-Currier dimerization of 1,1-disubstituted activated olefins derived from Morita-Baylis-Hillman adducts was observed in the presence of DABCO. The reaction is driven by the migration of an acyl group and produces multifunctionalized enol esters in yields greater than 90% in most cases, without necessitating column chromatographic purification. The acyl transfer is thought to proceed via a transition state typical of a Morita-Baylis-Hillman (MBH) reaction, supported by a brief mechanistic study involving computational calculations.
View Article and Find Full Text PDFAcc Chem Res
January 2023
Department of Chemistry, Korea Advanced Institute of Science & Technology (KAIST), Daejeon 34141, Republic of Korea.
alkaloids, composed of more than 100 members characterized by the compact tetracyclic scaffold, have fascinated the synthetic community with their structural diversity and notable bioactivities. On the basis of the structural phenotype, oligomerizations and oxidations are major biosynthetic diversification modes of the basic framework. Despite the rich history of synthesis of basic monomeric alkaloids, the synthesis of oligomeric alkaloids, as well as oxidized derivatives, has remained relatively unexplored because of their extra structural complexity.
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