TiCl catalyzed cleavage of (25R)-22-oxo-23-spiroketals. Synthesis of sapogenins with furostanol and pyranone E rings on the side chain.

Steroids

Instituto de Investigaciones Químico Biológicas, Universidad Michoacana de San Nicolás de Hidalgo, Ed.B-1, C.U., Morelia, Michoacán 58030, Mexico. Electronic address:

Published: December 2019


Category Ranking

98%

Total Visits

921

Avg Visit Duration

2 minutes

Citations

20

Article Abstract

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.

Download full-text PDF

Source
http://dx.doi.org/10.1016/j.steroids.2019.108488DOI Listing

Publication Analysis

Top Keywords

ticl catalyzed
4
catalyzed cleavage
4
cleavage 25r-22-oxo-23-spiroketals
4
25r-22-oxo-23-spiroketals synthesis
4
synthesis sapogenins
4
sapogenins furostanol
4
furostanol pyranone
4
pyranone rings
4
rings side
4
side chain
4

Similar Publications

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 PDF

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 PDF

A Mixed-Valence Ti(II)/Ti(III) Inverted Sandwich Compound as a Regioselective Catalyst for the Uncommon 1,3,5-Alkyne Cyclotrimerization.

Inorg 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.

Article Synopsis
  • The study outlines the synthesis and properties of a Ti(II)/Ti(III) inverted sandwich compound, beginning with a titanium(IV) precursor and its reduction through sodium metal to form a titanium(III) species.
  • Further reduction using lithium cyclopentyl leads to the formation of the mixed-valence Ti(II)/Ti(III) compound, confirmed by X-ray and EPR characterization.
  • The compound demonstrates effective catalytic activity for the cyclotrimerization of alkynes, utilizing a mechanism where two alkynes couple before a cycloaddition occurs, resulting in 1,3,5-substituted arenes.
View Article and Find Full Text PDF

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 PDF

β-Alkenylation of Saturated -Heterocycles via a C(sp)-O Bond Wittig-like Olefination.

J 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.

View Article and Find Full Text PDF