Recent Developments in the Palladium‐Catalyzed/Norbornene‐Mediated Synthesis of Carbo‐ and Heterocycles

Patel, Monak; Desai, Bhargav; Ramani, A.; Dholakiya, Bharatkumar Z.; Naveen, Togati

doi:10.1002/slct.202102641

Cited by 13 publications

(4 citation statements)

References 201 publications

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“…Usually, the benzo-fused rings constructed by Pd/NBE-promoted annulations are mainly based on complex multifunctional substrates or reagents, which are typically nontrivial to prepare . Motivated by these studies, we set out to develop Pd/NBE-promoted annulations between aryl iodides and the new types of bifunctional reagents that are simple and readily available (e.g., epoxides, aziridines, olefinic alcohol-containing alkylating reagents, etc.).…”

Section: Development Of New Annulations Based On Pd/nbe Cooperative C...mentioning

confidence: 99%

“…Interestingly, without an external terminating reagent, this chemistry can be extended to the synthesis of dihydrobenzofurans (DHBFs) under slightly modified conditions from Scheme (Scheme A) . Notably, N 1 is still the optimal cocatalyst for this reaction, and only 10 mol % is required, which, to the best of our knowledge, represents the lowest NBE cocatalyst loading in Catellani-type reactions. , It is worth mentioning that this method can be applied in the two-step synthesis of a 5-HT 2C receptor agonist family with 8-aryl-substituted DHBF as the common core structure (>200 members) (Scheme B) . Subjecting 2-aryl-substituted phenyl iodides 1e – g and commercially available chiral epoxide 2e to the standard reaction conditions, the desired chiral 2,3-dihydrobenzofuran products 13e – g were obtained in moderate to good yields.…”

Section: Development Of New Annulations Based On Pd/nbe Cooperative C...mentioning

confidence: 99%

“…Therefore, a series of effective strategies has been developed for the construction of benzo-fused skeletons . Among these methods, the annulation strategy based on palladium/norbornene (Pd/NBE) cooperative catalysis (also called the “Catellani reaction”) is pretty unique and promising. Pd/NBE cooperative catalysis, first introduced by Catellani in the 1990s, allows the sequential functionalization of ortho C–H and ipso C–I bonds of aryl iodides, thereby permitting expeditious syntheses of polysubstituted arenes.…”

Section: Introductionmentioning

confidence: 99%

“…The design of total synthesis strategies is deeply shaped by state-of-the-art reaction methodology development, and the overall synthetic efficiency of a synthetic route can be mainly determined by the key reactions used . We are deeply impressed by the power of Pd/NBE cooperative catalysis in the expeditious synthesis of polysubstituted arenes and benzo-fused rings . To achieve the efficient total synthesis of the representative target molecules in Figure A, we think it is highly desirable to invent new annulation methods to quickly assemble the common benzo-fused skeletons (e.g., isochroman, tetrahydroisoquinoline, indane, tetrahydronaphthalene, etc.).…”

Section: Introductionmentioning

confidence: 99%

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Benzo-Fused-Ring Toolbox Based on Palladium/Norbornene Cooperative Catalysis: Methodology Development and Applications in Natural Product Synthesis

2023

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Metrics & MoreArticle Recommendations CONSPECTUS: Benzo-fused skeletons are ubiquitous in agrochemicals, medicines, natural products, catalysts, and other organic function materials. The assembly of these skeletons in an efficient manner is an actively explored field in organic synthesis. Palladium/norbornene (Pd/NBE) cooperative catalysis is a powerful tool for the expeditious assembly of polysubstituted arenes through bisfunctionalization of the ortho and ipso positions of aryl iodides in one operation.Owing to the efforts of Lautens, Catellani, and others, an array of Pd/NBEpromoted annulations for the syntheses of diversified benzo-fused rings have been developed. However, these methods have not been broadly applied in total synthesis yet.Our group is interested in efficient and practical total synthesis of biologically active molecules. In the past 7 years, we have been devoted to the development of new annulation strategies for the assembly of common benzo-fused skeletons through Pd/NBE-promoted reactions of aryl iodides with novel bifunctional reagents. In this Account, we summarize our laboratory's systematic efforts in this direction. First, readily available epoxides and aziridines were exploited as versatile bifunctional alkylating reagents, which enables quick assembly of a series of valuable benzo-fused heterocycles, including isochromans, dihydrobenzofurans, 1,3-cis-tetrahydroisoquinolines (THIQs), 1,3-trans-THIQs, etc. Second, a convergent access to 5−7-membered benzo-fused carbocycles (including indanes and tetrahydronaphthalenes) was developed by Pd/NBE-promoted annulation of aryl iodides with simple olefinic alcohol-containing alkylating reagents. Third, a Pd/NBE-promoted annulation between aryl iodides and cyclohexanone-containing amination reagents was developed for the construction of benzo-fused N-containing bridged scaffolds. Thus, we have established a practical and versatile toolbox for the quick assembly of diversified benzo-fused skeletons. These new annulation reactions are of high chemo-, regio-, and stereoselectivities with good step and atom economy. Moreover, they are able to rapidly increase molecular complexity from simple building blocks. Finally, their synthetic value has been demonstrated by immediate adoption in several efficient total syntheses of medicines and complex natural products. Compared to conventional synthetic logics, the Pd/NBE-promoted annulation toolbox allows the development of highly convergent strategies, which significantly improves the overall synthetic efficiency.We believe the results presented in this Account will have significant implications beyond our research. It can be envisaged that new Pd/NBE-promoted annulations as well as new applications in complex total synthesis will be revealed in the near future.

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Section: Development Of New Annulations Based On Pd/nbe Cooperative C...mentioning

confidence: 99%

Section: Development Of New Annulations Based On Pd/nbe Cooperative C...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Benzo-Fused-Ring Toolbox Based on Palladium/Norbornene Cooperative Catalysis: Methodology Development and Applications in Natural Product Synthesis

2023

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Pd/Cu Co‐Catalyzed ortho‐Arylation of Aryl Iodides via Radical Intermediates with Aryl Diazonium Salts

Fu,

Guo,

Chen

et al. 2023

Adv Synth Catal

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A Cu/Pd co‐catalyzed Catellani‐type ortho arylation reaction of iodoarenes with aryl diazonium salts has been developed. Aryl radicals that derived from aryl diazonium salts were regioselectively installed at ortho position of iodoarenes via palladium catalyzed C−H activation. Mechanistic studies showed that, in contrast to classical Pd0−PdII−PdIV−PdII−Pd0 catalytic cycle, this radical cascades performed via a Pd0−PdII−PdIII−PdI−Pd0 cycle.

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Recent Advances in Cobalt‐catalyzed Functionalization of Unactivated Olefins

et al. 2022

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Olefins are low-cost starting materials that may be obtained in bulk quantities from petrochemical feedstocks and renewable resources. The transition metal-catalyzed unactivated olefin functionalization is well explored and received an extensive interest from synthetic chemists. In recent times, chemists have successfully employed different transition metals for the functionalization of unactivated olefins. Among the different transition metals that have been used, cobalt catalysts have received great attention from synthetic chemists for CÀ H functionalization reactions, owing to their ready availability and high reactivity. Herein, we discuss the most recent reports in the field of cobaltcatalyzed functionalization of unactivated olefins that enable CÀ C, CÀ X and CÀ hetero bond formation and covers the literature from 2016 to 2021.

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Recent Developments in the Palladium‐Catalyzed/Norbornene‐Mediated Synthesis of Carbo‐ and Heterocycles

Cited by 13 publications

References 201 publications

Benzo-Fused-Ring Toolbox Based on Palladium/Norbornene Cooperative Catalysis: Methodology Development and Applications in Natural Product Synthesis

Benzo-Fused-Ring Toolbox Based on Palladium/Norbornene Cooperative Catalysis: Methodology Development and Applications in Natural Product Synthesis

Pd/Cu Co‐Catalyzed ortho‐Arylation of Aryl Iodides via Radical Intermediates with Aryl Diazonium Salts

Recent Advances in Cobalt‐catalyzed Functionalization of Unactivated Olefins

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