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

Marine natural products.

Multicomponent reactions (MCRs) are fundamentally different from two-component reactions in several aspects. Among the MCRs, those with isocyanides have developed into popular organic-chemical reactions in the pharmaceutical industry for the preparation of compound libraries of low-molecular druglike compounds. With a small set of starting materials, very large libraries can be built up within a short time, which can then be used for research on medicinal substances. Due to the intensive research of the last few years, many new backbone types have become accessible. MCRs are also increasingly being employed in the total synthesis of natural products. MCRs and especially MCRs with isocyanides offer many opportunities to attain new reactions and basic structures. However, this requires that the chemist learns the “language” of MCRs, something that this review wishes to stimulate.

Multicomponent Reactions with Isocyanides.

Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has seen widespread success involves the use of a proximal heteroatom that serves as a directing group for the selective functionalization of a specific C-H bond. In a survey of examples of heteroatom-directed Rh catalysis, two mechanistically distinct reaction pathways are revealed. In one case, the heteroatom acts as a chelator to bind the Rh catalyst, facilitating reactivity at a proximal site. In this case, the formation of a five-membered metallacycle provides a favorable driving force in inducing reactivity at the desired location. In the other case, the heteroatom initially coordinates the Rh catalyst and then acts to stabilize the formation of a metal-carbon bond at a proximal site. A true test of the utility of a synthetic method is in its application to the synthesis of natural products or complex molecules. Several groups have demonstrated the applicability of C-H bond functionalization reactions towards complex molecule synthesis. Target-oriented synthesis provides a platform to test the effectiveness of a method in unique chemical and steric environments. In this respect, Rh-catalyzed methods for C-H bond functionalization stand out, with several syntheses being described in the literature that utilize C-H bond functionalization in a key step. These syntheses are highlighted following the discussion of the method they employ.

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Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

Green Chemistry is a relatively new emerging field that strives to work at the molecular level to achieve sustainability. The field has received widespread interest in the past decade due to its ability to harness chemical innovation to meet environmental and economic goals simultaneously. Green Chemistry has a framework of a cohesive set of Twelve Principles, which have been systematically surveyed in this critical review. This article covers the concepts of design and the scientific philosophy of Green Chemistry with a set of illustrative examples. Future trends in Green Chemistry are discussed with the challenge of using the Principles as a cohesive design system (93 references).

Green Chemistry: Principles and Practice

N-Heterocyclic Carbenes in Late Transition Metal Catalysis

UDP-N-acetylmuramyl-pentapeptide (UDP-MurNAc-pentapeptide) is well known to be a key intermediate of bacterial peptidoglycan biosynthesis. We first detected the occurrence of UDP-MurNAc-pentapeptide in the cyanobacterium Anabaena cylindrica (NIES-19), and identified the structure of this pentapeptide by two-dimensional 1H-1H and 1H-13C NMR correlation experiments and mass spectra.

Occurrence and identification of UDP-N-acetylmuramyl-pentapeptide from the cyanobacterium Anabaena cylindrica.

2-Benzyloxycarbonylamino-2-deoxy-D-ribose was conveniently synthesized via α-chloro-β-hydroxyester prepared from 2,3-O-isopropylidene-D-glyceraldehyde and ethoxyacetylene by the stereoselective aldol reaction

A stereoselective synthesis of 2-amino-2-deoxy-d-ribose

An chiral RhII -catalyzed cyclooligomerization reaction of thiophenes having triazolyl and vinyl substituents at the 2- and 4-positions was studied. Structurally interesting cyclic trimers, having chirality that is ascribed only to the orientation of the 2,4-disubstituted thiophene rings, are obtained. The 2,4-disubstitution of the starting thiophene monomer allows production of each of the enantiomers. The observed electronic circular-dichroism spectra are in accord with those simulated by density-functional theory calculations.

Chiral Macrocycles Having C3 Symmetry Resulting from Orientation of Thiophene Rings.

β-Xylofuranosides are stereoselectively synthesized in good yields by the successive treatment of the thiocarbonate, derived from 3,5-di-O-benzyl-D-xylofuranose, with methyl fluorosulfonate and hydroxy compounds in the presence of cesium fluoride.

A new method for the stereoselective synthesis of β-xylofuranoside

The silyl substituent of 3-silylcyclobutene prefers inward rotation rather than out- ward rotation during a thermal ring-opening reaction, giving the Z-isomer predominantly. This intriguing behavior was explained by assuming electron-accepting interactions between the low-lying σ*-orbital of the silicon-carbon linkage and the highest occupied molecular or- bital (HOMO) of the opening cyclobutene system, which are possible only in the inward tran- sition state. On the basis of this finding, a novel method for the stereoselective synthesis of functionalized 1,3-butadiene derivatives from cyclobutenones was developed. Boryl sub- stituents exhibit even stronger preference for inward rotation than silyl substituents as a re- sult of electron delocalization from the cyclobutene HOMO into the vacant p-orbital of boron at the inward transition state.

Masahiro Murakami

Papers

Occurrence and identification of UDP-N-acetylmuramyl-pentapeptide from the cyanobacterium Anabaena cylindrica.

A stereoselective synthesis of 2-amino-2-deoxy-d-ribose

Chiral Macrocycles Having C3 Symmetry Resulting from Orientation of Thiophene Rings.

A new method for the stereoselective synthesis of β-xylofuranoside

Torque control by metal-orbital interactions