Guangbin Dong

• University of Texas at Austin

Concise total syntheses of five leuconoxine‐type alkaloids, i.e., chloromelodinine, leuconodine A, leuconodine F, melodinine E, and leucinixine, are achieved through a pyrrole‐centered strategy. The approach features a newly developed palladium/norbornene‐catalyzed pyrrole double C−H functionalization reaction to generate the core skeleton and a di...

Concise total syntheses of five leuconoxine‐type alkaloids, i.e., chloromelodinine, leuconodine A, leuconodine F, melodinine E, and leuconoxine, are achieved through a pyrrole‐centered strategy. The approach features a newly developed palladium/norbornene‐catalyzed pyrrole double C─H functionalization reaction to generate the core skeleton and a di...

Despite the recent advancement, Matteson‐type reactions are almost exclusively used to construct linear molecules. Herein we report an iterative boron‐homologation approach to construct various carbocycles from a single precursor. This method utilizes an electron‐withdrawing group (EWG) as a handle to enable intramolecular Matteson‐type couplings,...

Despite the recent advancement, Matteson‐type reactions are almost exclusively used to construct linear molecules. Herein we report an iterative boron‐homologation approach to construct various carbocycles from a single precursor. This method utilizes an electron‐withdrawing group (EWG) as a handle to enable intramolecular Matteson‐type couplings,...

While the palladium/norbornene (Pd/NBE) cooperative catalysis has become increasingly useful for arene functionalization, its substrate scope has been mainly restricted to reactive aryl iodides and bromides. Despite being a more available and attractive feedstock, common aryl chlorides have not been used as substrates for the Pd/NBE catalysis. Here...

While the palladium/norbornene (Pd/NBE) cooperative catalysis has become increasingly useful for arene functionalization, its substrate scope has been mainly restricted to reactive aryl iodides and bromides. Despite being a more available and attractive feedstock, common aryl chlorides have not been used as substrates for the Pd/NBE catalysis. Here...

The directing group-based strategy has been highly effective for site-selective functionalization of alkenes, carbonyls, C−H bonds, C−C bonds, etc., but not yet known for unactivated aromatic π-systems. On the other hand, catalytic hydrogenation of arenes to the corresponding saturated carbo- or heterocycles provides a straightforward approach to i...

Fabricating organic semi-conducting materials into large-scale well-organized architectures is critical for building high performance molecular electronics. While graphene nanoribbons (GNRs) hold enormous promise for various device applications, their assembly into a well-structured monolayer or multilayer architecture poses a substantial challenge...

Concerted nucleophilic substitution, known as SN2 reaction, is a fundamental organic transformation used in synthesis to introduce new functional groups and construct carbon–carbon and carbon–heteroatom bonds¹. SN2 reactions typically involve backside attack of a nucleophile to the σ* orbital of a C(sp³)–X bond (X = halogen or other leaving group),...

Boron-mediated homologation can potentially access almost any kind of chiral centers from readily available boronates via asymmetric carbenoid insertion, followed by versatile transformations of the carbon−boron bonds. However, the current asymmetric boron homologation strategies exhibit limitations, and enantioselective insertion of diversely subs...

Constructive functionalization of unstrained aryl–aryl bonds has been a fundamental challenge in organic synthesis due to the inertness of these bonds. Here we report a split cross-coupling strategy that allows twofold arylation with diverse aryl iodides through cleaving unstrained aryl–aryl bonds of common 2,2′-biphenols. The reaction is catalysed...

Preparation of diverse homologs from lead compounds has been a common and important practice in medicinal chemistry. However, homologation of carboxylic acid derivatives, particularly amides, remains challenging. Here we report a hook-and-slide strategy for homologation of tertiary amides with tunable lengths of the inserted carbon chain. Alkylatio...

Scalable fabrication of graphene nanoribbons with narrow band gaps has been a nontrivial challenge. Here, we have developed a unique approach to access narrow band gaps by using hybrid edge structures. Bottom-up liquid-phase synthesis of bent N=6/8 armchair graphene nanoribbons (AGNRs) has been achieved in high efficiency through copolymerization b...

1,2-Azaborines represent a unique class of benzene isosteres that have attracted interest for developing pharmaceuticals with better potency and bioavailability. However, it remains a long-standing challenge to prepare monocyclic 1,2-azaborines, particularly multi-substituted ones, in an efficient and modular manner. Here we report a straightforwar...

Methods that can simultaneously install multiple different functional groups to heteroarenes via C−H functionalizations are valuable for complex molecule synthesis, which, however, remain challenging to realize. Here we report the development of vicinal di‐carbo‐functionalization of indoles in a site‐ and regioselective manner, enabled by the palla...

Methods that can simultaneously install multiple different functional groups to heteroarenes via C−H functionalizations are valuable for complex molecule synthesis, which, however, remain challenging to realize. Here we report the development of vicinal di‐carbo‐functionalization of indoles in a site‐ and regioselective manner, enabled by the palla...

Oxygen-substituted arenes widely exist in biologically important molecules and can serve as versatile handles to install other functional groups. However, direct and site-selective installation of oxygen groups to common aromatic compounds remains challenging, especially when additional arene functionalization is simultaneously required. Current ar...

Synthesis of sequence-defined monodisperse π-conjugated polymers with versatile backbones remains a substantial challenge. Here we report the development of an integrated iterative binomial synthesis (IIBS) strategy to enable backbone engineering of conjugated polymers with precisely controlled lengths and sequences as well as high molecular weight...

Herein we report the development of deacylative thiolation of diverse methyl ketones. The reaction is redox‐neutral, and heavy‐metal‐free, which provides a new way to introduce thioether groups site‐specifically to unactivated aliphatic positions. It also features excellent functional group tolerance and broad substrate scope, thus allowing late‐st...

Herein we report the development of deacylative thiolation of diverse methyl ketones. The reaction is redox‐neutral, and heavy‐metal‐free, which provides a new way to introduce thioether groups site‐specifically to unactivated aliphatic positions. It also features excellent functional group tolerance and broad substrate scope, thus allowing late‐st...

Given the emerging demand to "escape from flatland" for drug discovery, synthetic methods that can efficiently construct complex three-dimensional structures with multi-stereocenters become increasingly valuable. Here, we describe the development of Rh(I)-catalyzed intramolecular annulations between cyclobutanones and 1,5-enyne groups to construct...

Transition-metal-catalyzed C-C activation has become synthetically valuable; however, it rarely involves single-electron downstream processes. To expand the repertoire of C-C activation, here we describe the discovery of a Rh-catalyzed enantioselective C-C activation involving migration of a sulfonyl radical. This reaction directly transforms cyclo...

Herein, we describe a unique one‐carbon ring‐expansion strategy to access multi‐substituted 2‐indanones from benzocyclobutenones and styrene‐type olefins. The use of a cationic “ligandless” rhodium catalyst was the key for both high reactivity and selectivity towards the (4+1) product. Broad functional group tolerance, a good substrate scope, and s...

Herein, we describe a unique one‐carbon ring‐expansion strategy to access multi‐substituted 2‐indanones from benzocyclobutenones and styrene‐type olefins. The use of a cationic “ligandless” rhodium catalyst was the key for both high reactivity and selectivity towards the (4+1) product. Broad functional group tolerance, a good substrate scope, and s...

A new reaction mode of palladium/norbornene (Pd/NBE) cooperative catalysis is reported involving the selective coupling of two different carbon‐based electrophiles for vicinal double C‐H functionalization of five‐membered heteroarenes in a site‐selective and redox‐neutral manner. The key is to use alkynyl bromides as the second electrophile, which...

Careful choreography for a ketone shift Chemists devote tremendous effort to the precise placement of oxygens in molecular frameworks. Wu et al . report a convenient method to shift the oxygen in a carbonyl group to an adjacent carbon center. After activation of the oxygen to an alkenyl triflate, cooperative catalysis by palladium and norbornene ad...

In this article a new reaction mode of palladium/norbornene (Pd/NBE) cooperative catalysis is reported involving the selective coupling of two different carbon‐based electrophiles for vicinal double C−H functionalization of five‐membered heteroarenes in a site‐selective and redox‐neutral manner. The key is to use alkynyl bromides as the second elec...

Ketone functionalization is a cornerstone of organic synthesis. Herein, we describe the development of an intermolecular C−H alkenylation of enamides with the feedstock chemical vinyl acetate to access diverse functionalized ketones. Enamides derived from various cyclic and acyclic ketones reacted efficiently, and a number of sensitive functional g...

Herein, we report a [5+2] cycloaddition between readily accessible 1‐indanones and internal alkynes through Rh‐catalyzed activation of less strained C−C bonds. The reaction is enabled by a strongly σ‐donating NHC ligand and a carefully modified temporary directing group. A wide range of functional groups is tolerated, and the method provides straig...

An iridium-catalyzed C−H alkenylation of enamides with vinyl acetate has been developed as a versatile approach to diverse ketone functionalization (see scheme). The method exhibits broad substrate scope and high chemoselectivity. It also features a reaction pathway involving 1,2-Ir-C migratory insertion and syn-β-acetoxy elimination. Abstract Ket...

The Rh-catalyzed intermolecular [5+2] annulation between 1-indanones and alkynes is reported. It provides a rapid and straightforward entry to benzocycloheptenones. DFT calculation reveals the beneficial π–π interactions between the ligand and the substrate in the turnover-limiting migration insertion step. Abstract Herein, we report a [5+2] cyclo...

Herein, we describe the development of a deconstructive strategy for the first asymmetric synthesis of (−)‐thebainone A, capitalizing on an enantioselective C−C bond activation and a C−O bond cleavage reaction. The rhodium‐catalyzed asymmetric “cut‐and‐sew” transformation between sterically hindered trisubstituted alkenes and benzocyclobutenones al...

Herein, we report the synthesis of C3,C4-disubstituted indoles via the palladium/norbornene cooperative catalysis. Utilizing N-benzoyloxy allylamines as the coupling partner, a cascade process involving ortho-amination and ipso-Heck cyclization takes place with ortho-substituted aryl iodides to afford diverse indole products. The reaction exhibits...

A deconstructive strategy involving the cleavage of relatively inert C−C and C−O bonds to build more complex scaffolds enabled the total synthesis of morphine alkaloid (−)‐thebainone A in 13 (and 14) steps from commercially available starting materials (see scheme). The rhodium‐catalyzed asymmetric carboacylation reaction was applied successfully t...

In this issue of Chem, Morandi and coworkers report an exciting reversible transfer hydroarylation between ketones and unstrained arylated alcohols. Through a Rh-catalyzed β-aryl elimination process, the aryl moiety “shuttles” from the alcohol to the ketone substrate, which provides a milder alternative to conventional Grignard and organolithium ad...

The construction of indole, indoline, and carbazole heterocycles has been of significant interest in the synthetic community over the last century due to their prevalence in natural products and other biologically active compounds. In particular for indoles, many conventional methods developed to date require highly pre-functionalized arene precurs...

Structurally complex π‐conjugated polymers hold great promise as key components in sensor and electronic devices; however, their syntheses have not been a trivial task. From a synthetic efficiency perspective, it would be more attractive to access these materials using convenient and efficient methods from simple building blocks. One such synthetic...

Palladium/norbornene (Pd/NBE) cooperative catalysis has received enormous attention and found numerous synthetic applications in the past two decades. Considering the critical roles that NBE plays in the catalytic cycle, the use of structurally modified NBEs (smNBEs), starting from 2015, has become an important approach to address limitations and m...

A mechanistically guided approach is developed to predict electrophile compatibility in the palladium/norbornene (Pd/NBE) cooperative catalysis for the ipso and ortho difunctionalization of aryl halides. A key challenge in these reactions is to identify orthogonal electrophile and aryl halide starting materials that react selectively with different...

Carbon–carbon (C–C) bonds make up the skeletons of most organic molecules. The selective manipulation of C–C bonds offers a direct approach to editing molecular scaffolds but remains challenging. The kinetic inertness of C–C bonds can be overcome with transition-metal catalysis, which, nevertheless, relies on a substrate being highly strained or be...

Capitalized on versatile catalytic α,β-desaturation methods, strategies that directly functionalize carbonyl compounds at their less reactive β positions have emerged over the past decade. Depending on the reaction mechanism, general approaches include merging with conjugate addition, migratory coupling and redox cascade. This perspective provides...

Site-selective C-C bond formation through direct coupling of C(sp3)-H bonds with unsaturated hydrocarbons represents an atom-economical and redox-neutral way for functionalizing chemically inert positions, such as those β to a carbonyl group. While most existing β-functionalization methods utilize a directing group (DG) strategy, here we report a P...

An unexpected ortho-Heck reaction has been discovered during the study of palladium/norbornene (Pd/NBE) catalysis. Under the Catellani reaction conditions in the presence of lithium salts and olefins, Heck coupling takes place at the ortho position instead of the commonly observed ipso position; meanwhile, a norbornyl group is introduced at the are...

All-carbon tetrasubstituted olefins have been found in numerous biologically important compounds and organic materials. However, regio- and stereocontrolled construction of this structural motif still constitutes a significant synthetic challenge. Here, we show that a modular and regioselective synthesis of all-carbon tetrasubstituted olefins can b...

Herein we report a direct vicinal difunctionalization of thiophenes via the palladium/norbornene (Pd/NBE) cooperative catalysis. A series of mono- and disubstituted thiophenes can be difunctionalized site- and regio-selectively at the C4 and C5 positions in good yields, enabled by an arsine ligand and a unique amide-based NBE. The synthetic utility...

Graphene nanoribbons (GNRs) —an emerging family of carbon-based semiconductors — can be precisely synthesised from small molecules such as benzene derivatives through bottom-up approaches. This review outlines a summary of the development of bottom-up synthesis of GNRs in liquid phase. The strategies are classified based on edge structures and widt...

Poly-substituted aromatic sulfur compounds are widely found in pharmaceuticals, agrochemicals and organic materials. However, the position that a sulfur moiety can be introduced to is largely restricted to a pre-functionalized site; otherwise, use of electronically biased substrates or auxiliary groups that direct catalysis is required. Here we rep...

Here we describe a palladium-catalyzed intramolecular α-allylic alkylation of unactivated ketones with alkynes. The reaction proceeds in the absence of any amine cocatalyst; both endo and exo-bridged cyclohexanone bicycles can be obtained diastereoselectively. The stereodivergency is controlled by the ligand and acid additive used. Specifically, th...

Palladium/norbornene cooperative catalysis has emerged as a distinct approach to construct polyfunctionalized arenes from readily available starting materials. This Review provides a comprehensive overview of this field, including the early stoichiometric investigations, catalytic reaction developments, as well as the applications in the syntheses...

A direct β-alkenylation of simple ketones with alkenyl bromides is reported via a Pd-catalyzed redox cascade strategy. The reaction is redox neutral and directing-group-free, in the absence of strong acids or bases. Both cyclic and linear ketones are suitable substrates, and various alkenyl bromides can be coupled. The resulting β-alkenyl ketones a...

To expand the synthetic platform of the palladium-norbornene cooperative catalysis, here we report a general ortho thiolation of aryl and heteroaryl iodides using sulfenamides as a new class of electrophiles. The sulfenamides derived from a ε- ^t butyl-lactam were found most efficient to introduce various aryl and methyl sulfur groups at...

Palladium/norbornene (Pd/NBE) cooperative catalysis, also known as the Catellani reaction, has become an increasingly useful method for site-selective arene functionalization; however, certain constraints still exist because of its intrinsic mechanistic pathway. Herein, we report a redox-neutral ortho functionalization of aryl boroxines via Pd/NBE...

A three-step preparation of a highly water-soluble poly(p-phenylene ethynylene) (PPE) from commercially available starting materials is disclosed. The palladium/norbornene-catalyzed AB-C-type polymerization has been developed, which enables installation of two piperazine meta side chains concurrently with the construction of the PPE backbone. The c...

To show the synthetic utility of palladium/norbornene (Pd/NBE) cooperative catalysis, here we report concise syntheses of indenone‐based natural products, pauciflorol F and acredinone A, which are enabled by direct annulation between aryl iodides and unsaturated carboxylic acid anhydrides. Compared to the previous indenone‐preparation approaches, t...

To show the synthetic utility of palladium/norbornene (Pd/NBE) cooperative catalysis, here we report concise syntheses of indenone‐based natural products, pauciflorol F and acredinone A, which are enabled by direct annulation between aryl iodides and unsaturated carboxylic acid anhydrides. Compared to the previous indenone‐preparation approaches, t...

The development of a general platinum‐catalyzed desaturation of N‐protected lactams, ketones, and lactones to their conjugated α,β‐unsaturated counterparts is reported. The reaction operates under mildly acidic conditions at room temperature or 50 °C. It is scalable and tolerates a wide range of functional groups. The complementary reactivity to th...

The development of a general platinum‐catalyzed desaturation of N‐protected lactams, ketones, and lactones to their conjugated α,β‐unsaturated counterparts is reported. The reaction operates under mildly acidic conditions at room temperature or 50 °C. It is scalable and tolerates a wide range of functional groups. The complementary reactivity to th...

Herein, we describe our initial development of an asymmetric Pd-catalyzed annulation between aryl iodides and racemic epoxides for synthesis of 2,3-dihydrobenzofurans using a chiral norbornene cocatalyst. A series of enantiopure...

Achieving site-selectivity in arene functionalization that is complementary to the site-selectivity from electrophilic aromatic substitution reactions has been a long-standing quest in organic synthesis. Palladium/norbornene cooperative catalysis potentially offers a unique approach to this problem, but its use has been hampered by the ortho constr...

Herein, we report a palladium-catalyzed directed C-H arylation of protected thiols at the γ aliphatic sites. The key is to utilize Michael acceptors as a dual reagent to install a protecting/directing group on thiols via the thiol-Michael click reaction, which later can be easily removed under basic conditions. The C-H arylation proceeds with high...

Herein, we report a palladium‐catalyzed directed C‐H arylation of protected thiols at the γ aliphatic sites. The key is to utilize Michael acceptors as a dual reagent to install a protecting/directing group on thiols via the thiol‐Michael click reaction, which later can be easily removed under basic conditions. The C‐H arylation proceeds with high...

Palladium/norbornene (Pd/NBE) cooperative catalysis has emerged as a useful tool for preparing poly-substituted arenes; however, its substrate scope has been largely restricted to aryl iodides. While aryl bromides are considered as standard substrates for Pd-catalyzed cross coupling reactions, their use in Pd/NBE catalysis remains elusive. Here we...

Herein, we report the palladium/norbornene cooperatively catalyzed polymerization, which simplifies synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2B2C‐type multicomponent polymerization is developed using ortho‐amination/ipso‐alkynylation reaction for preparing various amine‐functionalized arylacetylene...

Herein, we report the palladium/norbornene cooperatively catalyzed polymerization, which simplifies synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2B2C‐type multicomponent polymerization is developed using ortho‐amination/ipso‐alkynylation reaction for preparing various amine‐functionalized arylacetylene...

Despite the great promise of armchair graphene nanoribbons (aGNRs) as high-performance semiconductors, practical band-gap engineering of aGNRs remains an unmet challenge. Given that width and edge structures are the two key factors for modulating band-gaps of aGNRs, a reliable synthetic method that allows control of both factors would be highly des...

Herein we report a full article about the detailed design and development of two palladium-catalyzed redox cascade methods that enable direct β-arylation of ketones. Palladium-catalyzed ketone dehydrogenation, aryl-X bond activation and conjugate addition were merged into a redox-neutral catalytic cycle. Non-metal-based aryl electrophiles were used...

Divergent total syntheses of enmein‐type natural products, (‐)‐enmein, (‐)‐isodocarpin and (‐)‐sculponin R, have been achieved in a concise fashion. Key features of the strategy include (a) an efficient early‐stage cage formation to control succeeding diastereoselectivity, (b) an one‐pot acylation/akylation/lactonization to construct the C‐ring and...

Divergent total syntheses of enmein‐type natural products, (‐)‐enmein, (‐)‐isodocarpin and (‐)‐sculponin R, have been achieved in a concise fashion. Key features of the strategy include (a) an efficient early‐stage cage formation to control succeeding diastereoselectivity, (b) an one‐pot acylation/akylation/lactonization to construct the C‐ring and...

Organotransition metal complexes capable of forming metalloradicals have been an intriguing subject of study for the past fifty years. Of these, rhodium porphyrin complexes have proven particularly interesting due to their straightforward synthesis and unique reactivity; indeed, these complexes are responsible for some highly influential transforma...

The application of exo -type directing groups (DGs) has led to the discovery of a wide range of novel C(sp ³ )–H activation methods, which allow efficient and site-selective functionalization of alcohol and amide derivatives.

Herein, we describe the development of a catalytic intramolecular "cut-and-sew" transformation between cyclobutanones and alkynes to construct cyclohexenone-fused rings. The challenge arises from the need for selective coupling at the more sterically hindered proximal position, which can be addressed using an electron-rich but less bulky phosphine...

Herein, we describe the development of a catalytic intramolecular "cut-and-sew" transformation between cyclobutanones and alkynes to construct cyclohexenone-fused rings. The challenge arises from the need for selective coupling at the more sterically hindered proximal position, which can be addressed using an electron-rich but less bulky phosphine...

Divergent total syntheses of enmein-type natural products, (–)-enmein, (–)-isodocarpin and (–)-sculponin R, have been achieved in a concise fashion. Key features of the strategy include (a) an efficient early-stage cage formation to control succeeding diastereoselectivity, (b) an one-pot acylation/akylation/lactonization to construct the C-ring and...

A Co(0)-catalyzed intramolecular alkyne/benzocyclobutenone coupling through C-C cleavage of benzocyclobutenones is described. Co2(CO)8/P[3,5-(CF3)2C6H3]3 was discovered to be an effective metal/ligand combination, which exhibits complementary catalytic activity to the previously established rhodium catalyst. In particular, the C8-substituted substr...

We report a Rh(I)-catalyzed site-selective coupling between ketone β C(sp3)-H bonds and aliphatic alkynes using an in-situ-installed directing group (DG). Upon hydrogenation or hydration, various β-alkylation or β-aldol products of the ketones are obtained with broad functional group tolerance. Mechanistic investigations support the involvement of...

On our path to the perfection of organic synthesis lies the challenge of controlling site selectivity, which is the differentiation of reactivity among the same kind of functional groups. Overcoming this challenge would significantly enhance synthetic efficiency and minimize waste production, which in turn calls for the development of new catalysts...

Alkylation reactions represent an important organic transformation to form C-C bonds. In addition to conventional approaches with alkyl halides or sulfonates as alkylating agents, the use of unactivated olefins for alkylations has become attractive from both cost and sustainability viewpoints. This Review summarizes transition-metal-catalyzed alkyl...

A range of aliphatic primary amines are site-selectively arylated in the γ-position using diaryl iodonium salts, and the products are isolated as the N-benzoylated derivatives in moderate to high yields.

Aryl carboxylic acid derivatives are ubiquitously found in pharmaceuticals, agrochemicals, and natural products. They also serve as common building blocks for access to other functional groups. Here, we describe a unique method for direct preparation of multi-functionalized aromatic carboxylic esters from simple readily available aryl iodides via p...

A new hydrazone-based exo-directing group (DG) strategy is developed for the functionalization of unactivated primary β C—H bonds of aliphatic amines.

This method gives access to a variety of novel, pharmaceutically interesting polycyclic lactams.

The temperature required to induce cross-linking in typical benzocyclobutene-based thermosets is near 250 °C, which exceeds the use temperature of many chemical components. A new and versatile synthesis of BCB-functionalized monomers has allowed access to monomers that can be incorporated into a variety of macromolecular platforms to enable signifi...

No abstract is available for this article.

Direct mono-α-C—H arylation of cyclopentanones with a variety of aryl bromides is achieved using a palladium/amine catalyst system.

Described is a new hydrazone-based exo-directing group (DG) strategy developed for the functionalization of unactivated primary β C-H bonds of aliphatic amines. Conveniently synthesized from protected primary amines, the hydrazone DGs are shown to site-selectively promote the β-acetoxylation and tosyloxylation via five-membered exo-palladacycles. A...

A general and practical catalytic method has been developed for the rapid synthesis of HCTD (heptacyclo[6.6.0.0(2,6).0(3,13).0(4,11).0(5,9).0(10,14)]tetradecanes) and various new 7,12-disubstituted HCTDs from norbornadienes. Compared to the known approaches, this new protocol avoids stoichiometric metals, utilizes commercially available reagents as...

This Catellani-type C—H arylation is enabled by isopropyl carbonate anhydrides (II) and (IV), which serve as both an acyl cation and a hydride source.

Direct arylation of cyclopentanones has been a long-standing challenge because of competitive self-aldol condensation and multiple arylations. Reported herein is a direct mono-α-CH arylation of cyclopentanones with aryl bromides which is enabled by palladium/amine cooperative catalysis. This method is scalable and chemoselective with broad function...

The first decarbonylative cycloaddition of less-strained cyclic ketones (isatins) with isocyanates is reported. Initiated by C-C activation, this distinct [5 - 2 + 2] transformation provides a rapid entry to access various benzimidazolidinone derivatives, and a wide range of isocyanates can be efficiently coupled with broad functional group toleran...

Herein we describe the first enantioselective Rh-catalyzed carboacylation of oximes (imines) via C-C activation. In this transformation, the benzocyclobutenone C1-C2 bond is selectively activated by a low valent rhodium catalyst and subsequently the resulting two Rh-C bonds add across a C=N bond, which provides a unique approach to access chiral la...