Organocatalytic Enantioselective Desymmetrization of Prochiral 2,2‐Disubstituted Cyclic 1,3‐Diones

Chegondi, Rambabu; Patel, Srilaxmi M.; Maurya, Sundaram; Donthoju, Ashok

doi:10.1002/ajoc.202100180

Cited by 19 publications

(9 citation statements)

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“…Thus, we disclose our latest findings on manganese(I)-catalyzed in situ dienylation and cascade diastereoselective desymmetrization-based intramolecular Diels–Alder reaction using iso -pentadienyl carbonate-linked cyclohexadienones 1 to access diverse homo-aryl 6/6/5-fused tricyclic natural product scaffolds [Scheme c, ( 4 or 5 )]. Prochiral cyclohexadienones are versatile substrates used in various desymmetrizations based on stereoselective transformations. − Especially, rhodium(III)-catalyzed C(sp 2 )–H arylative-cascade cyclization of 1,6-enynes and allenyls derived from cyclohexadiene were employed to obtain stereoselective cyclic molecules. Despite significant advancement in this area, manganese(I)-catalyzed C(sp 2 )–H activation of 2-phenylpyridines and 2-pyrimidyl indoles respectively via an arylation/intramolecular conjugate addition of 1,6-enynes provided hydrobenzofuran derivatives.…”

Section: Introductionmentioning

confidence: 99%

Robust Synthesis of Terpenoid Scaffolds under Mn(I)-Catalysis

et al. 2023

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The 6/6/5-fused tricyclic scaffold is a central feature of structurally complex terpenoid natural products. A stepeconomical cascade transformation that leads to a complex molecular skeleton is regarded as a sustainable methodology. Therefore, we report the first Mn(I)-catalyzed C(sp 2 )−H chemoselective in situ dienylation and diastereoselective intramolecular Diels−Alder reaction using iso-pentadienyl carbonate to access 6/6/5-fused tricyclic scaffolds. To the best of our knowledge, there is no such report thus far to utilize iso-pentadienyl carbonate as a substrate in C−H activation catalysis. Extensive mechanistic studies, such as the isolation of catalytically active organo-manganese(I) complexes, 1,3-dienyl-intermediates, and isotopic labeling experiments have supported the proposed mechanism of this cascade reaction.

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Section: Introductionmentioning

confidence: 99%

Robust Synthesis of Terpenoid Scaffolds under Mn(I)-Catalysis

et al. 2023

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“…We recently reported a method for the desymmetrization of a 1,3-cyclopentanedione moiety via the intramolecular aldol reaction of rac-aldehyde 9 with DL-proline (Scheme 1a). 14,15 This reaction involves the formation of an intramolecular hydrogen bond between a carbonyl group in the 1,3cyclopentanedione and the carboxylic group of enamine intermediate 10, derived from (R)-9 and L-proline, or (S)-9 and D-proline (not shown in Scheme 1a), to afford bicyclic compound 11 in 73% yield along with a trace amount of its diastereomer, 12. The stereochemistries of the two contiguous angular centers in 12 correspond to those in 3, which inspired us to develop this methodology for the total synthesis of 3.…”

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confidence: 99%

Total Synthesis of (+)-Coriamyrtin via a Desymmetrizing Strategy Involving a 1,3-Cyclopentanedione Moiety

et al. 2023

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We describe the total synthesis of (+)-coriamyrtin, which bears a highly functionalized cis-hydrindane skeleton and is a widely known neurotoxin of the Coriariaceae family. Our synthetic strategy involves the highly stereoselective construction of the cishydrindane skeleton via a desymmetrizing strategy involving a 1,3cyclopentanedione moiety using an intramolecular aldol reaction and the formation of the 1,3-diepoxide moiety of coriamyrtin through the elaborate functionalization of the cyclopentane ring in the bicyclic structure. P icrotoxane-type sesquiterpenes are widely distributed in plants, such as Coriariaceae, Orchidaceae, and Menispermaceae. 1 Since picrotoxin, which is a poisonous compound composed of a 1:1 mixture of picrotoxinin (1) and picrotin (2), was found in Menispermum cocculus in 1818, more than 130 picrotoxane-type natural products have been isolated (Figure 1). 2 Because 1 is a strong antagonist of the γ-

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“…Enantioselective desymmetrization is an effective strategy for generating chiral compounds from prochiral precursors, which has been extensively studied in the construction of functionalized molecules with complex structures via the chemical or biocatalytic desymmetrization process . Recently, the desymmetric protocols have been successfully applied for different transformation reactions using 1,3-diones, cyclohexadienones, diols, dicarboxylic acid derivatives, three- and four-membered ring compounds, etc. It is worth noting that the alkynyl groups are optimal candidates for desymmetric transformation due to their diverse conversion modes.…”

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confidence: 99%