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

Marine natural products.

The biaryl structural motif is a predominant feature in many pharmaceutically relevant and biologically active compounds. As a result, for over a century 1 organic chemists have sought to develop new and more efficient aryl -aryl bond-forming methods. Although there exist a variety of routes for the construction of aryl -aryl bonds, arguably the most common method is through the use of transition-metalmediated reactions. 2-4 While earlier reports focused on the use of stoichiometric quantities of a transition metal to carry out the desired transformation, modern methods of transitionmetal-catalyzed aryl -aryl coupling have focused on the development of high-yielding reactions achieved with excellent selectivity and high functional group tolerance under mild reaction conditions. Typically, these reactions involve either the coupling of an aryl halide or pseudohalide with an organometallic reagent (Scheme 1), or the homocoupling of two aryl halides or two organometallic reagents. Although a number of improvements have developed the former process into an industrially very useful and attractive method for the construction of aryl -aryl bonds, the need still exists for more efficient routes whereby the same outcome is accomplished, but with reduced waste and in fewer steps. In particular, the obligation to use coupling partners that are both activated is wasteful since it necessitates the installation and then subsequent disposal of stoichiometric activating agents. Furthermore, preparation of preactivated aryl substrates often requires several steps, which in itself can be a time-consuming and economically inefficient process.

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Heck-Type-lautens.pdf

Aryl-aryl bond formation by transition-metal-catalyzed direct arylation.

4.3. Reaction Mechanism 2373 4.4. Asymmetric Synthesis 2374 4.5. Outlook 2374 5. Alternating Polymerization of Oxiranes and CO2 2374 5.1. Reaction Outlines 2374 5.2. Catalyst 2376 5.3. Asymmetric Polymerization 2377 5.4. Immobilized Catalysts 2377 6. Synthesis of Urea and Urethane Derivatives 2378 7. Synthesis of Carboxylic Acid 2379 8. Synthesis of Esters and Lactones 2380 9. Synthesis of Isocyanates 2382 10. Hydrogenation and Hydroformylation, and Alcohol Homologation 2382

Transformation of carbon dioxide.

Electrochemistry represents one of the most intimate ways of interacting with molecules. This review discusses advances in synthetic organic electrochemistry since 2000. Enabling methods and synthetic applications are analyzed alongside innate advantages as well as future challenges of electroorganic chemistry.

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

The design and implementation of cascade reactions is a challenging facet of organic chemistry, yet one that can impart striking novelty, elegance, and efficiency to synthetic strategies. The application of cascade reactions to natural products synthesis represents a particularly demanding task, but the results can be both stunning and instructive. This Review highlights selected examples of cascade reactions in total synthesis, with particular emphasis on recent applications therein. The examples discussed herein illustrate the power of these processes in the construction of complex molecules and underscore their future potential in chemical synthesis.

Cascade reactions in total synthesis.

Cyclic carbonates are valuable compounds that have applications in a variety of chemical fields. Methodologies for the synthesis of cyclic carbonates are well investigated in recent years, and the most successful and popular procedure is the utilization of CO 2 . This paper presents recent progress in the synthesis of cyclic carbonates by a CO 2 -fixation process, which involves novel palladium-catalyzed CO 2 -recycling reactions.

Novel Methodologies for the Synthesis of Cyclic Carbonates

Synthesis of Carbapenem Antibiotics

Tf2NH, an organic acid, efficiently catalyzes (2 + 2) cycloaddition reactions of silyl enol ethers with acrylates or propiolate. The process affords highly substituted cyclobutanes in high yield with high stereoselectivity under practical and environmentally benign conditions. Application for the formation of terpene skeletons and multigram synthesis of four-membered carbocycles were demonstrated.

A practical catalytic method for preparing highly substituted cyclobutanes and cyclobutenes.

イミノケテンの環状付加反応 ii イミノケテンとアミドの縮合反応によるアルボリン,グリコスミニン,およびルテカルピンの全合成

A palladium-catalyzed CO2-recycling reaction has been developed. Reaction of 4-methoxycarbonyloxy-2-butyn-1-ols with phenols, carried out in the presence of a palladium catalyst, produces phenoxy-substituted cyclic carbonates by way of a pathway involving a CO2 elimination-fixation. A variety of propargylic alcohols and phenols participate in these reactions which yield cyclic carbonates with high efficiencies. Stereoselective construction of trans-cyclic carbonates is achieved by using nonsymmetric substrates. Highly enantioselective reactions occur when (S)-BINAP is used as a ligand. Reaction of 4-phenoxycarbonyloxy-2-butyn-1-ol in the presence of the palladium catalyst yields the corresponding cyclic carbonates via a three-component decomposition-reconstruction process.

A novel methodology for the synthesis of cyclic carbonates based on the palladium-catalyzed cascade reaction of 4-methoxycarbonyloxy-2-butyn-1-ols with phenols, involving a novel carbon dioxide elimination-fixation process.

Masataka Ihara

Papers

Novel Methodologies for the Synthesis of Cyclic Carbonates

Synthesis of Carbapenem Antibiotics

A practical catalytic method for preparing highly substituted cyclobutanes and cyclobutenes.

イミノケテンの環状付加反応 ii イミノケテンとアミドの縮合反応によるアルボリン,グリコスミニン,およびルテカルピンの全合成

A novel methodology for the synthesis of cyclic carbonates based on the palladium-catalyzed cascade reaction of 4-methoxycarbonyloxy-2-butyn-1-ols with phenols, involving a novel carbon dioxide elimination-fixation process.