Arene diazonium salts are common, easily prepared and highly useful intermediates in organic synthesis due to their rich reactivity diverse transformations. In this review, recent advances involving arene as starting materials or active for various synthetically applications summarized.

The transition metal-catalyzed "cut and sew" transformation has recently emerged as a useful strategy for preparing complex molecular structures. After oxidative addition of metal into carbon-carbon bond, the resulting two carbon termini can be both functionalized in one step via following migratory insertion reductive elimination with unsaturated units, such alkenes, alkynes, allenes, CO polar multiple bonds. Three- or four-membered rings are often employed reaction partners due to their...

Herein we report a highly meta-selective C–H arylation using simple tertiary amines as the directing group. This method takes advantage of Pd/norbornene catalysis, offering distinct strategy to control site selectivity. The reaction was promoted by commercially available AsPh3 ligand and unique "acetate cocktail". Aryl iodides with an ortho electron-withdrawing group were employed coupling partner. A wide range functional groups, including some heteroarenes, are tolerated under conditions....

A Pd and norbornene-catalyzed ortho-arene amination via Catellani-type C-H functionalization is reported. Aryl halides are used as substrates; N-benzoyloxyamines isopropanol employed the amine source (oxidant) reductant respectively. Examples provided in 50-99% yields with high functional group tolerance. This method gives complementary site selectivity at ortho- instead of ipso-position aryl halides.

Alkylation of carbonyl compounds is a commonly used carbon-carbon bond-forming reaction. However, the conventional enolate alkylation approach remains problematic due to lack regioselectivity, risk overalkylation, and need for strongly basic conditions expensive alkyl halide reagents. Here, we describe development ketone-alkylation strategy using simple olefins as alkylating agents. This employs bifunctional catalyst comprising secondary amine low-valent rhodium complex capable activating...

New modes of chemical reactivity are high value to synthetic organic chemistry. In this vein, carbon-carbon (C-C) activation is an emerging field that offers new possibilities for synthesizing valuable complex molecules. This review discusses the pioneering stoichiometric discoveries in up most recent applications apply catalytic transformations. Specifically, focuses on C-C relatively unstrained systems, including reactions, chelation-directed and chelation-free reactions. While systems...

Abstract Herein, we report the palladium‐catalyzed direct arylation of unactivated aliphatic C−H bonds in free primary amines. This method takes advantage an exo ‐imine‐type directing group (DG) that can be generated and removed situ. A range unprotected amines are suitable substrates, undergoing site‐selective at γ‐position. Methyl as well cyclic acyclic methylene groups activated. Furthermore, when aniline‐derived substrates were used, preliminary success with δ‐C−H was achieved. The...

We describe a Pd-catalyzed site-selective functionalization of unactivated aliphatic C-H bonds, providing chemically differentiated 1,2-diols from monoalcohol derivatives. The oxime was employed as both directing group (DG) and an alcohol surrogate for this transformation. As demonstrated in range substrates, the bonds β to are selectively oxidized. Besides activation methyl groups, methylene groups (CH(2)) cyclic substrates methine (CH) at bridge-head positions can also be functionalized....

Slipping boron into alkyl ethers The carbon–oxygen bonds that hold together are relatively inert. Lyu et al. report zinc and nickel can team up to insert between the carbon oxygen using an unusual mechanism. First, a dibromoborane pries open bond with help from ion. Next, stitches boron, oxidation of metallic starts cycle over again. Versatile reactivity at inserted center then add carbons original ether or swap out for nitrogen. Science , this issue p. 175

ConspectusBridged and fused rings are commonly found in biologically important molecules. Current tactics to construct these ring systems primarily based on stepwise formation (i.e., making one first followed by another) cycloaddition reactions (e.g., Diels–Alder reaction). To seek a complementary perhaps more unified ring-forming approach, deconstructive strategy C–C bond activation of cyclic ketones has been conceived. The named "cut-and-sew" reaction uses with tethered unsaturated moiety...

We report that nitrogen heterocycles can serve as competent nucleophiles in the palladium-catalyzed dynamic kinetic asymmetric alkylation of vinyl aziridines. The resulting alkylated products were obtained with high regio-, chemo-, and enantioselectivity. Both substituted 1H-pyrroles 1H-indoles successfully employed to give exclusively branched N-alkylated products. synthetic utility this process was demonstrated by applying method preparation several medicinal chemistry lead compounds...

Three catalysts create alcohols by guiding water to attack carbon-carbon bonds in the opposite sense than it normally would.

Cut and sew: A rhodium-catalyzed regioselective carboacylation reaction of benzocyclobutenones was developed (see scheme). Directed by the pendant olefins, C1C2 bond is selectively cleaved rather than C1C8 bond. Subsequent alkene insertion leads to complex fused-ring systems. This provides facile access natural-product-like polycyclic structures in a chemoselective atom-economic fashion. Detailed facts importance specialist readers are published as "Supporting Information". Such documents...

Here we report the first highly enantioselective Rh-catalyzed carboacylation of olefins via C–C bond activation benzocyclobutenones. Good yields and excellent enantioselectivities (92–99% ee, 14 examples) were obtained for substrates with various steric electronic properties. In addition, fully saturated poly-fused rings prepared from products through a challenging catalytic reductive dearomatization approach. These investigations provide distinct way to prepare chiral carbon frameworks that...

Allgegenwärtige und vielseitige Ketogruppen können eine palladiumkatalysierte ortho-Hydroxylierung von Arenen steuern, die ausgehend einfachen Arylketonen einen effektiven Zugang zu o-Acylphenolen bietet. Außerdem wird Pd-katalysierte oxidative ortho-Carbonylierung mit Keto-Steuergruppe vorgestellt, ein Ketal-Lacton liefert. BTI=PhI(TFA)2 Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset....