Switchable 1,2-Rearrangement Enables Expedient Synthesis of Structurally Diverse Fluorine-Containing Scaffolds

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(26), P. 11626 - 11637

Published: May 23, 2022

Skeletal rearrangement that changes the connectivity of molecule via cleavage and reorganization carbon–carbon bonds is a fundamental powerful strategy in complex molecular assembly. Because lack effective methods to control migratory tendency different groups, achieving switchable selectivity skeletal has been long-standing quest. Metal-based dyotropic provides unique opportunity address this challenge. However, remains unexplored. Herein, we show such problem could be solved by modifying ligands on metal catalyst changing oxidation states aptitude thereby providing ligand-controlled, strategy. Experimental density functional theory calculation studies prove rational design. The occurs only when nickel(II) intermediate reduced more nucleophilic nickel(I) species, sterically hindered iPrPDI ligand facilitates 1,2-aryl/Ni rearrangement, while terpyridine promotes 1,2-acyl/Ni rearrangement. This method allows site-selective activation C–C applied for divergent synthesis four medicinally relevant fluorine-containing scaffolds from same starting material.

Language: Английский

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C–C Bond Cleavage of α-Pinene Derivatives Prepared from Carvone as a General Strategy for Complex Molecule Synthesis

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(5), P. 746 - 758

Published: Feb. 16, 2022

ConspectusThe preparation of complex molecules (e.g., biologically active secondary metabolites) remains an important pursuit in chemical synthesis. By virtue their sophisticated architectures, natural products inspire total synthesis campaigns that can lead to completely new ways building molecules. In the twentieth century, one such paradigm which emerged was use naturally occurring "chiral pool terpenes" as starting materials for These inexpensive and abundant provide easily accessed source enantioenriched material enantiospecific products. The most common applications chiral terpenes are syntheses where structure can, entirely or largely, be superimposed directly onto a portion target structure. Less straightforward uses, terpene is not immediately evident target, more challenging implement. Nevertheless, these "nonintuitive" approaches illustrate ultimate promise pool-based strategies: any single could applied indefinite number structurally diverse synthetic targets.By definition, strategies require carefully orchestrated sequences C–C bond forming cleaving reactions result remodeling architecture. combination traditional rearrangement chemistry transition-metal-catalyzed cleavage methods, latter were primarily developed early twenty-first rich powerful toolbox implementing this approach. Account, we detail our efforts variety tactics skeletal carvone, terpene. This strategy enabled reorganization carvone scaffold into intermediates with carboskeletons, we, then, leveraged disparate products.We begin by describing initial investigations various, mechanistically distinct processes involving cyclobutanols synthesized from carvone. studies showcased how electrophile-mediated semipinacol rearrangements [2.2.1]bicyclic intermediates, Rh- Pd-catalyzed densely functionalized cyclohexenes pertinent product We, present several using beginning bridged, polycyclic sesquiterpenoid longiborneol, carvone-derived [2.2.1]bicycle following key rearrangement. Next, discuss members macrocyclic phomactin family cyclohexene derivative prepared through Rh-catalyzed reaction. Finally, describe marine diterpene xishacorene B, cleavage/cross-coupling facilitated assembly core [3.3.1]bicycle resident

Language: Английский

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Palladium‐Catalyzed Stereoselective Cleavage of C−P Bond: Enantioselective Construction of Atropisomers Containing a P‐Stereogenic Center

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: Sept. 28, 2022

The transition-metal-catalyzed C-P bond cleavage has emerged as a powerful tool for the formation of both C-C and bond. However, stereoselective is still undeveloped. Herein, we report palladium-catalyzed construction P-stereogenic phosphines stereogenic axis. This protocol enables quick synthesis atropisomers bearing center in high yields, diastereo- enantioselectivities up to 98 % ee, >25 : 1 dr. product able serve chiral catalyst phosphine catalyzed [3+2] cycloaddition allenoates imines, showing great potential present methodology.

Language: Английский

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Recent advances in the reactions of silacyclobutanes and their applications

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(10), P. 2840 - 2855

Published: Jan. 1, 2022

This review summarizes the growing landscape in reactions of silacyclobutanes (SCBs) by highlighting fascinating progress, deconstructing mechanistic underpinnings, and drawing insight from related ring-opening expanding SCBs.

Language: Английский

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State-of-the-Art Advances in Enantioselective Transition-Metal-Mediated Reactions of Silacyclobutanes

Synthesis, Journal Year: 2022, Volume and Issue: 54(24), P. 5400 - 5408

Published: Aug. 23, 2022

Abstract Studies on the enantioselective transformation of silacyclobutanes (SCBs) have become an emerging topic in recent decade, due to feature high ring strain, and manageable Si–C bond cleavage formation. This short review summarizes remarkable achievements asymmetric transition-metal-mediated reaction benzosilacyclobutanes, resulting carbon- or silicon-stereogenic organosilanes with functional substituents. 1 Introduction2 Asymmetric Transition-Metal-Catalyzed Ring Expansion Reaction3 Ring-Opening Reaction4 Conclusion Outlook

Language: Английский

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Transition-Metal-Catalyzed C–C Bond Formation from C–C Activation

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(21), P. 2867 - 2886

Published: Oct. 26, 2023

ConspectusC-C single bonds are ubiquitous in organic compounds. The activation and subsequent functionalization of C-C provide a unique opportunity to synthesize conventionally inaccessible molecules through the rearrangement carbon skeletons, often with favorable atom step economy. However, thermodynamically kinetically inert. Consequently, is particularly attractive yet challenging field chemistry. In past decade, we sought develop efficient strategies carry out transition-metal-catalyzed diverse cleavage/C-C forming reactions obtain some insights into intrinsic reactivities different bonds. With our efforts, readily available alcohols, carboxylic acids, ketones served as suitable substrates for catalytic coupling reactions, which reviewed this Account. 2009, observed Ni-catalyzed cross aryl nitriles arylboronic esters C-CN cleavage. Encouraged by these results, interested bond activation. Due their broad availability, then turned attention cleavage acids. Rhodium-catalyzed decarbonylative acids (hetero)arenes was achieved oxidative addition situ formed, more reactive mixed anhydrides Rh(I) without need oxidants that commonly required decarboxylative Subsequently, decarbonylation unstrained realized under Rh catalysis assisted N-containing directing groups. Following work, group exchange 2-fold By employing chelation strategy, Rh-catalyzed secondary benzyl alcohols also accomplished β-carbon elimination rhodium alcoholate intermediates. competing oxidation via β-hydrogen same intermediates suppressed five-membered rhodacycles formed after elimination. Different types transformations including Heck-type reaction alkenes, arylsilanes, Grignard-type aldehydes or imines, have been achieved, showing great potential formation These bond-forming complementary traditional couplings halides organometallic reagents. produce small byproducts. To improve economy, investigated strained-ring cyclic intermolecular cyclization benzocyclobutenones alkynes recently uncommon C1-C8 removable blocking strategy. intramolecular annulation benzocyclobutenols achieved. summary, developments demonstrate new further expand synthetic utility activation, efforts substrate scope achieve earth-abundant metal-catalyzed transformations.

Language: Английский

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Photoelectrochemical asymmetric dehydrogenative [2 + 2] cycloaddition between C–C single and double bonds via the activation of two C(sp3)–H bonds

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(12), P. 1186 - 1193

Published: Nov. 6, 2023

Language: Английский

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Prospects and challenges for nitrogen-atom transfer catalysis

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(6), P. 424 - 438

Published: April 13, 2023

Language: Английский

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A cyclase that catalyses competing 2 + 2 and 4 + 2 cycloadditions

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(2), P. 177 - 184

Published: Jan. 23, 2023

Language: Английский

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Photoredox catalysis harvesting multiple photon or electrochemical energies

Beilstein Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 19, P. 1055 - 1145

Published: July 28, 2023

Photoredox catalysis (PRC) is a cutting-edge frontier for single electron-transfer (SET) reactions, enabling the generation of reactive intermediates both oxidative and reductive processes via photon activation catalyst. Although this represents significant step towards chemoselective and, more generally, sustainable chemistry, its efficacy limited by energy visible light photons. Nowadays, excellent alternative conditions are available to overcome these limitations, harvesting two different but correlated concepts: use multi-photon such as consecutive photoinduced electron transfer (conPET) combination photo- electrochemistry in synthetic photoelectrochemistry (PEC). Herein, we review most recent contributions fields activations organic functional groups. New opportunities chemists captured, selective reactions employing super-oxidants super-reductants engage unactivated chemical feedstocks, scalability up gram scales continuous flow. This provides comparisons between techniques (multi-photon photoredox PEC) help reader fully understand their similarities, differences potential applications therefore choose which method appropriate given reaction, scale purpose project.

Language: Английский

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