Tandem Prins cyclization for the synthesis of 1,8-dioxa-3-azaspiro[4.5]dec-2-ene derivatives

Reddy, L. Madhava; Satteyyanaidu, Vallabhareddy; Lakshmi, Jerripothula K.; Reddy, Ch. Krishna; Reddy, B. V. Subba

doi:10.1016/j.tetlet.2018.01.075

Cited by 7 publications

(2 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1,3-Dioxanes, for example, can be synthesized with an excess of suitable aldehyde in presence of an acid catalyst. 12 It has been well established that either strong Lewis (e.g., TiCl 4 , TiBr 4 , InCl 3 , SnCl 4 , BF 3 .OEt 2 ) [13][14][15][16][17][18] or Brønsted acids (e.g., H 2 SO 4 , trifluoroacetic acid, p-toluenesulfonic acid, triflic acid) [19][20][21][22] have to be employed to the effective synthesis of these heterocycles. Some studies have demonstrated that concomitant usage of both types of acid catalysts has positive synergistic effect.…”

Section: Introductionmentioning

confidence: 99%

Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Fiorot

Rambabu²,

Vijayakumar

et al. 2019

J. Braz. Chem. Soc.

View full text Add to dashboard Cite

Density functional theory calculations (ωB97X-D/6-311++G(d,p)) are employed to investigate an alternative pathway for Prins-like cyclization. Although strong acids usually catalyze this reaction, 4-amino-1,3-dioxanes are rapidly obtained in high yields without catalyst when benzenamines and acetaldehyde react at low temperatures, in aqueous medium. Considering these conditions, we applied a supermolecule model with explicit water molecules to compute the mechanism for 4-amino-1,3-dioxanes formation from the reactants. The structure of the primary solvation shell was determined by Metropolis Monte Carlo method. In the Prins-cyclization step, we found an unpredicted pathway with non-ionic transition structures or intermediates. Explicit water molecules establish a net of hydrogen bonds allowing prototropism, maintaining the electrical neutrality in the system while two protons transfer occurs. To provide data to further experimental confirmation of this hypothesis, we estimated the kinetic isotope effect for the reaction. We also investigated the use of aliphatic amines, which indicates that the reaction may be of a broader application than first observed experimentally.

show abstract

Section: Introductionmentioning

confidence: 99%

Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Fiorot

Rambabu²,

Vijayakumar

et al. 2019

J. Braz. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…Therefore, we assumed that the allyl acetate moiety of annsellanes could be accessed more efficiently using prefunctionalized homoallyl alcohols (Figure B). To date, several heteroatom-substituted homoallyl alcohols, such as hydroxy, N -tosyl, N -nosyl, and amide-substituted alcohols, have been used in Prins cyclization. However, there have been no reports on the use of acetoxy- or chloro-substituted homoallylic alcohols in Prins cyclization (Figure C).…”

mentioning

confidence: 99%

Total Synthesis of Ansellone G and Phorbadione

et al. 2022

View full text Add to dashboard Cite

The first total synthesis of marine sesterterpenoid ansellone G (2) was accomplished. This strategy utilizes the Prins cyclization reaction of a chloro-substituted homoallyl alcohol to synthesize the hydrobenzopyran skeleton. The preintroduction of the chloro groups facilitated the functional group transformation for 2 after constructing the carbon framework. Furthermore, we also successfully synthesized phorbadione (3) by dehydrating the tertiary alcohol. The HIV latency-reversing activity of the synthesized 2, 3, and deacetylated 2 was also evaluated.

show abstract

Six-Membered Ring Systems: With O and/or S Atoms

Santos¹,

Silva²

2020

Progress in Heterocyclic Chemistry

View full text Add to dashboard Cite

This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). NoticesKnowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

show abstract

Tandem Prins cyclization for the synthesis of 1,8-dioxa-3-azaspiro[4.5]dec-2-ene derivatives

Cited by 7 publications

References 27 publications

Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Total Synthesis of Ansellone G and Phorbadione

Six-Membered Ring Systems: With O and/or S Atoms

Contact Info

Product

Resources

About