Herein is disclosed an efficient enantio- and diastereoselective spiroketalization of aromatic ketone tethered to -homoformyl and enone moiety via enol formation using quinine derived squaramide organocatalyst to access aromatic [6,5] spiroketals with complete atom economy. Furthermore, aromatic spiroketals undergo Brønsted acid catalyzed Piancatelli type rearrangement to provide dihydronaphtho[1,2-]furans with retention of the enantioselectivities.
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http://dx.doi.org/10.1021/acs.orglett.2c00074 | DOI Listing |
J Am Chem Soc
July 2024
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontier Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
Transition metal-catalyzed enantioselective hydroamination of 1,3-dienes provides a direct methodology for the construction of chiral allylamines. So far, all of the reported examples used nucleophilic amines and proceeded with 3,4-regioselectivity. Herein, we describe the first example of nickel-catalyzed enantioselective 1,4-hydroamination of 1,3-dienes using trimethoxysilane and hydroxylamines with a structurally adaptable aromatic spiroketal based chiral diphosphine (SKP) as the ligand, affording a wide array of α-substituted chiral allylamines in high yields with excellent regio- and enantioselectivities.
View Article and Find Full Text PDFChem Biodivers
March 2024
Phytochemistry Division, CSIR-Central Institute of Medicinal and Aromatic Plants (CIMAP), PO CIMAP, Lucknow, 226015, India.
Artemisia pallens Wall. ex DC (Asteraceae) is cultivated for the production of high-value essential oil from its aerial biomass. In this study, the chemical composition of the root (crop-residue) essential oil was investigated for the first time, using column-chromatography, GC-FID, GC-MS, LC-QTOF, and NMR techniques, which led to the identification of twenty constituents, with isolation of (E)-2-(2',4'-hexadiynylidene)-1,6-dioxaspiro [4.
View Article and Find Full Text PDFOrg Lett
January 2023
Shanghai Key Laboratory of Chemical Biology & School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. China.
An asymmetric cascade allylation/spiroketalization reaction between 2-(1-hydroxyallyl)phenols and 5-methyleneoxazolines is accomplished by using a chiral Ir(I) catalyst derived from commercially available iridium precursor and the Carreira ligand. This protocol furnishes a class of structurally novel and unique oxazoline-spiroketals in up to 86% yield, >99% ee and >20:1 dr. Moreover, control experiments reveal that 4,4-disubstitution on 5-methyleneoxazolines is necessary to avoid the aromatization and for the spiroketalization to occur.
View Article and Find Full Text PDFEng Microbiol
September 2022
Department of Natural Medicinal Chemistry and Pharmacognosy, School of Pharmacy, Qingdao University, Qingdao 266071, China.
Natural occurring aromatic polyketides from actinomycetes indicate a structurally and functionally diverse family of polycyclic polyphenols. Some of them are consequently suggested as lead structures for drug development. Among them, rubromycins are derived from a single C26 polyketide chain and exhibit an unusual bisbenzannulated [5,6]-spiroketal system that connects a highly oxygenated naphthazarin motif to an isocoumarin unit.
View Article and Find Full Text PDFChem Sci
June 2022
Pharmaceutical Biology, Department of Pharmaceutical Sciences, University of Basel Klingelbergstrasse 50 4056 Basel Switzerland
The often complex control of bacterial natural product biosynthesis typically involves global and pathway-specific transcriptional regulators of gene expression, which often limits the yield of bioactive compounds under laboratory conditions. However, little is known about regulation mechanisms on the enzymatic level. Here, we report a novel regulatory principle for natural products involving a dedicated acetyltransferase, which modifies a redox-tailoring enzyme and thereby enables pathway furcation and alternating pharmacophore assembly in rubromycin polyketide biosynthesis.
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