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

Marine natural products.

The direct functionalization of C-H bonds in organic compounds has recently emerged as a powerful and ideal method for the formation of carbon-carbon and carbon-heteroatom bonds. This Review provides an overview of C-H bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.

C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals

In studying the evolution of organic chemistry and grasping its essence, one comes quickly to the conclusion that no other type of reaction plays as large a role in shaping this domain of science than carbon-carbon bond-forming reactions. The Grignard, Diels-Alder, and Wittig reactions are but three prominent examples of such processes, and are among those which have undeniably exercised decisive roles in the last century in the emergence of chemical synthesis as we know it today. In the last quarter of the 20th century, a new family of carbon-carbon bond-forming reactions based on transition-metal catalysts evolved as powerful tools in synthesis. Among them, the palladium-catalyzed cross-coupling reactions are the most prominent. In this Review, highlights of a number of selected syntheses are discussed. The examples chosen demonstrate the enormous power of these processes in the art of total synthesis and underscore their future potential in chemical synthesis.

Palladium-catalyzed cross-coupling reactions in total synthesis.

4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

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.

Heating 2,3,5,6,7,8-hexamethylidenebicyclo[2.2.2]octane with an excess of C60 in toluene for 3–4 d gives the 1 : 3 multiple Diels–Alder adduct in low (ca. 10%) yield.

Extended Projection of C60 Spheres into Three-Dimensional Space-Three- Fold Cycloaddition of (60) Fullerene to Hericene.

Unusual photoisomerization of an "encased" .alpha.-diketone

The sequential condensation of diisopropyl squarate with a vinyl anion and a lithium acetylide triggers a cascade of mechanistic events that eventuates in formation of highly functionalized unsaturated diquinanes.

Acetylide Anions Exert Complete Control over Aldolization During the Direct Conversion of Squarate Esters into Polyquinanes.

An enantioselective route to the decahydro-as-indacene15 is described. Anionic oxy-Cope rearrangement of alcohol 5 initiates the sequence, which capitalizes on thermodynamics to control ultimate elaboration of the four key stereogenic centers resident in the several intermediates.

Synthetic Studies on Spinosyn A. Convenient Enantioselective Construction of a Suitably Functionalized trans,anti,cis-Decahydro-as- indacene Intermediate via (3.3) Sigmatropy and Double Configurational Inversion.

The unprotected 2- and 3-hydroxycyclohexanones 1−8 were prepared by methods that skirted as much as possible their proclivity for α-ketol rearrangement (where the possibility for such isomerization...

Evaluation of Chelation Effects Operative During Diastereoselective Addition of the Allylindium Reagent to 2‐ and 3‐Hydroxycyclohexanones in Aqueous, Organic, and Mixed Solvent Systems.

Leo A. Paquette

Papers

Extended Projection of C60 Spheres into Three-Dimensional Space-Three- Fold Cycloaddition of (60) Fullerene to Hericene.

Unusual photoisomerization of an "encased" .alpha.-diketone

Acetylide Anions Exert Complete Control over Aldolization During the Direct Conversion of Squarate Esters into Polyquinanes.

Synthetic Studies on Spinosyn A. Convenient Enantioselective Construction of a Suitably Functionalized trans,anti,cis-Decahydro-as- indacene Intermediate via (3.3) Sigmatropy and Double Configurational Inversion.

Evaluation of Chelation Effects Operative During Diastereoselective Addition of the Allylindium Reagent to 2‐ and 3‐Hydroxycyclohexanones in Aqueous, Organic, and Mixed Solvent Systems.