https://pubs.rsc.org/en/content/articlepdf/2019/NP/C8NP00092A

Marine natural products.

Ionic liquids in catalysis

10. Patented Literature 2616 10.1. Esterification 2616 10.2. Ether Formation 2619 10.2.1. Etherification without Cyclization 2619 10.2.2. Etherification with Cyclization 2624 10.3. N-Alkylation 2625 10.4. Other Reactions 2627 11. Summary and Outlook 2628 12. Note Added in Proof 2628 13. Abbreviations Used in This Review 2629 14. Acknowledgments 2629 15. Supporting Information Available 2630 16. References 2630

Mitsunobu and Related Reactions: Advances and Applications

This Review describes the application of nitroxides to synthesis and polymer chemistry. The synthesis and physical properties of nitroxides are discussed first. The largest section focuses on their application as stoichiometric and catalytic oxidants in organic synthesis. The oxidation of alcohols and carbanions, as well as oxidative C-C bond-forming reactions are presented along with other typical oxidative transformations. A section is also dedicated to the extensive use of nitroxides as trapping reagents for C-centered radicals in radical chemistry. Alkoxyamines derived from nitroxides are shown to be highly useful precursors of C-centered radicals in synthesis and also in polymer chemistry. The last section discusses the basics of nitroxide-mediated radical polymerization (NMP) and also highlights new developments in the synthesis of complex polymer architectures.

Nitroxides: applications in synthesis and in polymer chemistry.

Simple indole alkaloids and those with a nonrearranged monoterpenoid unit

Fluorous phase chemistry: a new industrial technology

A versatile and high-yielding indium trichloride mediated cyclization reaction of silylated homoallylic alcohols, thiols, or amines with aldehydes or epoxides is described as a rapid route to a range of unsaturated heterocycles. The excellent diastereoselectivity observed offers a method of wide scope and generality.

A versatile indium trichloride mediated Prins-type reaction to unsaturated heterocycles.

The growing impetus to develop greener and more cost-efficient synthetic methods has prompted Chemists to look for new ways to activate small organic molecules. Among them, electrosynthesis is one of the greenest and cheapest since it is possible to perform redox reactions without the need for any chemical reagents. Even though electrosynthesis is on the verge of a resurgence, it is far from being a new discipline. In fact, organic electrosynthesis was popularised by Manual Baizer in the early 60s while working at Monsanto. In this article, we will review the major, as well as the most recent, achievements in industrial organic electrosynthesis.

/pdf/organic-electrosynthesis-from-academia-to-industry-1fzsccy8k8.pdf

Organic electrosynthesis: From academia to industry

https://dobbsgroupqm.files.wordpress.com/2011/03/the-silyle28093prins-reaction-a-novel-method-for-the-synthesis-of-dihydropyrans.pdf

The silyl-Prins reaction: a novel method for the synthesis of dihydropyrans

[Introduction] The Bartoli indole synthesis is the treatment of an ortho-substituted nitro-aromatic compound with 3 equiv of vinylmagnesium bromide to give the 7-substituted indole,1,2 and this method has rapidly become the shortest and most flexible synthesis for indoles of this substitution pattern.1-5 We have recently reported an extension to this methodology, suggesting that it may not be limited exclusively to the synthesis of 7-substituted indoles but that modest yields of other substitution patterns may also be obtained via this methodology.6 However, there is no doubt that the best yields are obtained when the nitro-aromatic compound possesses an ortho substituent, enforcing selectivity in the 3,3-sigmatropic rearrangement and subsequent cyclization step. This ortho substituent is, of course, undesirable in the synthesis of many indoles when a Bartoli approach may be advantageous. 

We have also been interested in the generation and use of heteroaryl free radicals for some time now and have reported the radical reactions and cyclizations of indoles bearing halogen substituents at both the 2- and 7-positions.3,7,8 

We envisaged a combination of these two methodologies, whereby a range of o-bromonitrobenzenes are treated under Bartoli conditions with various vinyl Grignard reagents (using the o-bromine atom to direct the cyclization) and then subsequently reduced using the heteroaryl radical methodology to replace the halogen and give a 7-unsubstituted indole, i.e., effectively using the bromine as a labile protecting group (Scheme 1). This method could give a significant reduction in the number of steps required for the synthesis of many complex indoles and also offers the advantage that many functionalities are tolerant to radical-generating conditions without the need for protection.

Adrian P. Dobbs

Papers

Fluorous phase chemistry: a new industrial technology

A versatile indium trichloride mediated Prins-type reaction to unsaturated heterocycles.

Organic electrosynthesis: From academia to industry

The silyl-Prins reaction: a novel method for the synthesis of dihydropyrans

Total synthesis of indoles from Tricholoma species via Bartoli/heteroaryl radical methodologies.