Abstract

The discovery of new synthetic methods and routes for making new bonds is one of the highest incentives to an organic chemist. Innovative, efficient, effective, economical and exceptionally environmentally friendly synthetic methods are being continuously discovered. Transition metal catalyzed C-H activation has been unearthed as one of these methods, especially iron catalyzed direct C-H activation. Fundamental to making more discoveries is understanding the mechanism behind a specific reaction. To this end, the mechanism behind iron catalyzed C-H activation was investigated. Results indicate the intermediary transition state for the iron species involves an Fe(I) species but the attempt to synthesize this Fe(I) species failed. We also confirmed that Fe(II) is definitely not the active species for this reaction. The nitrogen-based ligand might not have afforded us the Fe(I) complexes but there was evidence to show the reduction of the Fe(acac)3 due to the formation of the biphenyl product. In the same vein of discovery, we identified a mild, one-pot, FeCl2 mediated procedure to produce 3-substituted allylic alcohols from α,β-unsaturated ketones. The addition of an organolithium nucleophile produced tertiary allylic alcohol as an intermediate, which underwent a 1,3-OH migration assisted by FeCl2. The proposed mechanism indicates that a syn-facial migration occurs for the significant product and we obtained yield as high as 98% from this one-pot reaction. New synthetic methods are also very beneficial to the world outside chemistry. The study of the carcinogen 2-amino--carboline (AαC) and its interaction with DNA involved the synthesis of the AC-DNA adduct. We report the synthesis of AαC and 2-nitro-α-carboline (AαC-NO2) which also facilitate the synthesis of DNA adducts for biophysical studies. An attempt was made to synthesize the fluorinated 2-nitro-α-carboline which will enable the use of 19F-NMR for monitoring of these studies. Cyclization of the coupled product for the fluorinated analogue could not be achieved due to the electron deficiency in the ring systems. AαC was obtained in good yields of 88%, and the AαC-NO2 was obtained in 60% yield.

Highlights

  • Development of new innovative green methods for synthesis has been an intense driving force in recent times

  • EXPERIMENTAL SECTION Instrumentation: A Perkin-Elmer Lambda 1050 spectrometer was employed for obtaining UV/Vis spectra

  • NMR spectra were acquired with a Bruker Avance 300 MHz spectrometer The imine((E)-N,1-diphenylethan-1-imine and arylamine product ((E)-N-([1,1'-biphenyl]-2-yl)-1phenylethan-1-imine) were synthesized using the methods from previous work[31] Synthesis of Imine To an oven dried 50 mL RBF with a stir bar was added 20 g of 3 Å molecular sieves and 30 mL of toluene

Read more

Summary

GENERAL INTRODUCTION

In the field of organic and medicinal chemistry, synthetic routes to synthesize fine chemicals and materials are always being explored The goal for these disciplines is to find synthetic routes which are effective, efficient and economical. With the rise in environmental concerns about syntheses and processes, many of these synthetic routes incorporate either environmentally friendly methods or chemicals.[1] Fundamental to developing these synthetic routes, is understanding the mechanisms by which the active catalyst catalyzes the reaction of interest. Iron catalyzed C-H activation reactions have been identified as an economical, environmentally friendly and efficient method for synthesizing fine chemicals and materials.[2]. Though this method is well known and established, the mechanism through which these reactions happen under various conditions is not well understood, the need to investigate how iron catalyzes direct C-H activation in the presence of a Grignard. There is the need for the synthesis of DNA adducts of these carcinogen -- a research frontier identified through previous studies .6 It was found to be cost effective to synthesize the carcinogen of interest to be used for synthesis of the DNA adducts used for these biophysical studies the need to find quick, efficient and effective methods to synthesize these carcinogens

WHY C-H ACTIVATION?
SYNTHESIS OF 2-AMINO- -CARBOLINE AND ANALOGUES RELEVANT FOR DNA ADDUCT BIOPHYSICAL STUDIES
INTRODUCTION
RESULT
CONCLUSION
FECL2 MEDIATED REARRANGEMENT OF TERTIARY ALLYLIC ALCOHOLS
Findings
Full Text
Paper version not known

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.