Bioinspired Synthesis of Pinoxaden Metabolites Using a Site-Selective C-H Oxidation Strategy.

A bioinspired synthesis of Pinoxaden metabolites is described herein. A site-selective C-H oxidation strategy validated by density functional theory (DFT) calculations was devised for preparing metabolites . Oxidation of the benzylic C-H bond in tertiary alcohol using KSO and catalytic AgNO formed the desired metabolite that enabled access to metabolites and in a single step.

-Ammonium Ylide Mediators for Electrochemical C-H Oxidation.

The site-specific oxidation of strong C(sp)-H bonds is of uncontested utility in organic synthesis. From simplifying access to metabolites and late-stage diversification of lead compounds to truncating retrosynthetic plans, there is a growing need for new reagents and methods for achieving such a transformation in both academic and industrial circles. One main drawback of current chemical reagents is the lack of diversity with regard to structure and reactivity that prevents a combinatorial approach for rapid screening to be employed.

Bioinspired Synthesis of a Sedaxane Metabolite Using Catalytic Vanadyl Acetylacetonate and Molecular Oxygen.

A bioinspired synthesis of the sedaxane metabolite 2 from intermediate 3 using catalytic VO(acac)2 and O2 is described. Intermediate 3 was synthesized starting from 2-bromostyrene in four steps. The inner cyclopropyl ring of 3 was assembled with trans geometry using a highly diastereoselective Nishiyama cyclopropanation, and the outer hydroxycyclopropyl ring was installed using the Kulinkovich cyclopropanation.