A concise and general route to synthesize a new class of [6-5-6] tricyclic core embedded polyheterocycles has been accomplished using diastereoselective Nazarov cyclization with an overall yield of 35-40%. Versatility of this synthetic route has also been demonstrated by accessing a variety of [6-5-5] tricyclic core incorporated polycycles. It was observed that the efficiency of cyclization depends upon the impact of polarization on the reacting systems. Amongst the various Lewis and Brønsted acids screened for cyclization, triflic acid was found to be the most effective catalyst.

Download full-text PDF

Source
http://dx.doi.org/10.1039/b901632eDOI Listing

Publication Analysis

Top Keywords

nazarov cyclization
8
core embedded
8
tricyclic core
8
application nazarov
4
cyclization
4
cyclization access
4
access [6-5-6]
4
[6-5-6] [6-5-5]tricyclic
4
[6-5-5]tricyclic core
4
embedded heterocycles
4

Similar Publications

This manuscript describes a study of diverse reaction outcomes that stem from the ionization of -alkynyl-Prins adducts. Experimental results have demonstrated unexpected behavior in the nitrogen-containing systems compared to the analogous oxygen derivatives derived from -Prins/-Nazarov sequences. In-depth experimental studies and computational analysis revealed an intricate mechanism involving competing -Nazarov and -Nazarov pathways.

View Article and Find Full Text PDF

Steric Activation in the Nazarov Cyclization of Fully Substituted Divinyl Ketones.

Chemistry

December 2024

Medicinal Chemistry, Monash Institute of Pharmaceutical Sciences, Monash University, 381 Royal Parade, Parkville, Victoria, 3052, Australia.

Fully substituted divinyl ketones (fsDVKs) have long been regarded as resistant to Nazarov cyclization (NC) unless they contain strategically positioned electronically activating substituents. Here, however, we show that fsDVKs bearing only electronically neutral alkyl or aryl groups actually undergo facile NC due to steric crowding in the pentadienyl cation intermediate, which raises its energy and reduces the barrier height to cyclization. Strongly ionizing and suitably bulky acid moieties further increase the energy of this intermediate cation, favoring cyclization.

View Article and Find Full Text PDF

Bioinspired Total Synthesis of 3--Junipercedrol.

Org Lett

September 2024

School of Chemistry, Key Laboratory of Advanced Technologies of Material, Ministry of Education, Southwest Jiaotong University, Chengdu 610031, P. R. China.

A bioinspired total synthesis of 3--junipercedrol, which contains a strained tricyclo[5.2.2.

View Article and Find Full Text PDF

Expansion of Structure Property in Cascade Nazarov Cyclization and Cycloexpansion Reaction to Diverse Angular Tricycles and Total Synthesis of Nominal Madreporanone.

Angew Chem Int Ed Engl

December 2024

School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, Shanghai, 200240, China.

A cascade Nazarov cyclization/dicycloexpansions reaction was developed for the precise synthesis of the angularly fused M/5/N (M=5, 6; N=4-9, 13) tricyclic skeletons. The prioritized expansion of the first ring played a critical role in the transformations, due to the release of ring strain, and the nature of the substituents present on the substrate is another influencing factor. This pioneering cascade reaction features broad substrates scope (33 examples), short reaction time, exceptional yields (up to 95 %), and remarkable regioselectivities (>20 : 1).

View Article and Find Full Text PDF

Asymmetric Total Synthesis of Euphordraculoate A and Pedrolide.

Angew Chem Int Ed Engl

October 2024

College of Chemistry, Sichuan University, 29 Wangjiang Rd., Chengdu, Sichuan, 610064, China.

Here we report the asymmetric total syntheses of two rearranged tigliane diterpenoids, euphordraculoate A and pedrolide. A reductive dihydroxylation cascade and Nazarov cyclization were performed to generate euphordraculoate A, which was subjected to a cascade of Eu-promoted dienyl enolization, intramolecular Diels-Alder reaction and enol-ketone tautomerization to afford pedrolide, a pathway consistent with our proposal for the biogenesis of pedrolide.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!