The stereospecific substitution of non-derivatized and non-allylic enantioenriched alcohols with only water as a by-product would enable the use of readily available alcohols as substrates for green and sustainable transformations. However, the poor leaving group ability of the OH group has hampered the development of such a process. Denton and co-workers recently described the use of (2-hydroxybenzyl)diphenylphosphine oxide as a catalyst of a redox-neutral and zero-waste-generating Mitsunobu reaction. This innovative process constitutes the first intermolecular stereospecific substitution of non-allylic alcohols, and might find industrial applications.
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http://dx.doi.org/10.1002/anie.201911532 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Xi'an Jiaotong University, School of Chemical Engineering & Technology, Xingqing Road 28, 710049, Xi'an, CHINA.
The nickel catalyzed multi-component cross-electrophile carbonylation which emerges as a powerful and efficient method for constructing diverse ketones has attracted increasing attention of organic chemists. However, the selectivity of this reaction poses a significant challenge. In this work, we have developed a current-regulated selective nickel-catalyzed electroreductive cross-electrophile carbonylation, which offers a direct convergent synthesis of β/γ-hydroxy ketones, which represent pivotal structural motifs found in numerous natural products, bioactive molecules, pharmaceutical compounds, and essential building blocks.
View Article and Find Full Text PDFMed Chem Res
August 2024
Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211, United States.
We have developed convenient protocols for alkene disulfonoxylation, which involve stirring alkene substrate with a commercial I(III) oxidant and sulfonic acid in CHCl at ambient temperature. The reactions can be performed open to air without any special precautions to exclude moisture and, in most cases, deliver the products of vicinal disulfonoxylation. Where relevant, the reactions are stereospecific and furnish the products of -disulfonoxylation.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, Singapore 637371, Singapore.
Halogenophilic nucleophilic substitution (S2X) has a distinctly different reaction pathway compared to the bimolecular nucleophilic substitution reaction (S2), but they can lead to the same reaction product. However, their differences can be distinguished by studying stereoselective reactions in which both reaction pathways are possible. Herein, we utilize the stereospecific nature of S2 and the presence of a pro-chiral anion intermediate in S2X to conduct a quantitative study in which both S2 and S2X reactions exist.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Stereoselective alkene 1,2-difunctionalization is a privileged strategy to access three-dimensional C(sp)-rich chiral molecules from readily available "flat" carbon feedstocks. State-of-the-art approaches exploit chiral transition metal-catalysts to enable high levels of regio- and stereocontrol. However, this is often achieved at the expense of a limited alkene scope and reduced generality.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Hubei Research Center of Fundamental Science-Chemistry, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China.
Chiral tetrahydro-β-carbolines, as one of the most intriguing subtypes of indole alkaloids, have emerged as the privileged units in plenty of natural products and biologically active molecules with an impressive range of bioactive properties. However, the stereodivergent construction of these valuable skeletons containing multistereogenic centers from readily available starting materials remains very challenging, especially, in view of the introduction of an axial chirality. Herein, we developed an efficient method toward enantioenriched tetrahydro-β-carbolines with readily available tryptophan-derived aldimine esters and allylic carbonates under mild reaction conditions.
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