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The regioselective opening of the F ring of 22-oxo-23-spiroketals 7a-d using TiCl in acetic anhydride yielded the novel furostanols 11a-d along with cholestanic derivatives 8a-d with pyranone E ring. The structures of the new derivatives thus obtained were established using one- (DEPT) and two-dimensional H, C NMR experiments (COSY, HSQC, HMBC, NOESY). The 22α-hydroxyl orientation in compounds 11a-d was proposed by comparison of the C chemical shifts with those of other aglycone members of this family, and confirmed by combined NOESY and X-ray diffraction analysis of compound 11a.
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http://dx.doi.org/10.1016/j.steroids.2019.108488 | DOI Listing |
J Org Chem
June 2025
Department of Chemistry, Department of Medicinal Chemistry and Molecular Pharmacology, Purdue University, West Lafayette, Indiana 47907, United States.
We report highly diastereoselective TiCl-mediated tandem reactions that provide functionalized tricyclic benzocycloheptafurans in an efficient manner. The reaction of a range of substituted α-keto esters with dihydrofuran or phenyl dihydrofuran in CHCl set up a tandem reaction sequence, providing fused ring heterocycles. The precursor-substituted keto esters were synthesized efficiently by using a two-step sequence.
View Article and Find Full Text PDFPhys Chem Chem Phys
December 2024
Center for Computational Quantum Chemistry, University of Georgia, Athens, GA 30602, USA.
Density functional theory is employed in understanding the reactivity in the TiCl catalyzed Friedel-Crafts benzylation of benzene with substituted benzyl chlorides in nitromethane solvent. A series of ten substituted (in the aromatic ring) benzyl chlorides are characterized by theoretical reactivity indices. The theoretical parameters are juxtaposed to experimental relative rates of benzylation.
View Article and Find Full Text PDFInorg Chem
May 2024
Departamento de Química Orgánica y Química Inorgánica, Instituto de Investigación Química "Andrés M. del Río" (IQAR), Universidad de Alcalá, Campus Universitario, Alcalá de Henares, Madrid E-28805, Spain.
Org Lett
April 2024
Department of Organic Synthesis & Process Chemistry, Council of Scientific and Industrial Research (CSIR)-Indian Institute of Chemical Technology (IICT), Hyderabad 500007, India.
This study presents a total synthesis and revision of the stereochemical configuration of the conformationally flexible natural product benzo[]isochromene stereodiad alongside its diastereomeric counterparts. The highlights of the synthesis are the TiCl-mediated diastereoselective aldol reaction, Pd-catalyzed lactonization, and Schmidt glycosidation. Our efforts using total synthesis disclosed herein proved that a previously assigned structure required revision.
View Article and Find Full Text PDFJ Org Chem
February 2024
Centro de Investigación de la Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla (BUAP), 14 Sur Esq. San Claudio, Col. San Manuel, 72570 Puebla, México.
Although the C-H functionalization of -heterocycles is, in fact, an easy chemical transformation, the C-H functionalization is, on the contrary, a quite difficult chemical process. Here, we present a two-step protocol that allows the ready conversion of pyrrolidines, piperidines, and an azepane into their corresponding 3--alkenyl lactams via the transient formation of 3-alkoxyamino lactams followed by a Wittig-like C(sp)-O bond olefination with stabilized ylides from phosphonium salts mediated by -BuOK. Additionally, as a proof of the synthetic effectiveness of this novel methodology, the first synthesis of the natural product callylactam A was achieved through a TiCl-catalyzed double bond isomerization of a 3--alkenyl 2-piperidone to its isomer.
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