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.

Model approach to the pentagonal dodecahedrane. synthesis and properties of a monoseco derivative

1(5)-Cyanosemibullvalene from barrelene. Spectral and crystal structure analysis of the marked equilibrium preference exerted by an efficient .pi.-electron acceptor substituent

Small-Ring Annulation and Ring Expansion of the Dodecahedrane Framework. Homododecahedranone and the 21-Homododecahedryl Cation.

Total Synthesis of Natural (+)-Acetoxycrenulide.

We report a diastereoselective synthesis of 2 containing the core structure of the entire eastern sector of sanglifehrin A. The route proceeds by directed chain extension of appropriate building blocks, their timely convergent amalgamation, and ultimate coupling to a preformed tripeptide subunit.

Leo A. Paquette

Papers

Model approach to the pentagonal dodecahedrane. synthesis and properties of a monoseco derivative

1(5)-Cyanosemibullvalene from barrelene. Spectral and crystal structure analysis of the marked equilibrium preference exerted by an efficient .pi.-electron acceptor substituent

Small-Ring Annulation and Ring Expansion of the Dodecahedrane Framework. Homododecahedranone and the 21-Homododecahedryl Cation.

Total Synthesis of Natural (+)-Acetoxycrenulide.

Highly Diastereocontrolled Synthesis of the C1—C25 Domain of Sanglifehrin A.