Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 4702 - 4707
Published: Jan. 1, 2024
An asymmetric difluoroalkylation using α,α-difluoroenol as the key synthon has been disclosed, providing oxindoles containing a chiral quaternary carbon center in generally good yields and with excellent stereoselectivities.
Language: Английский
Advanced Science, Journal Year: 2024, Volume and Issue: 11(14)
Published: Feb. 6, 2024
A robust and practical difluoroalkylation synthon, α,α-difluoroenol species, which generated in situ from trifluoromethyl diazo compounds water the presence of dirhodium complex, is disclosed. As compared to presynthesized difluoroenoxysilane formed difluoroenolate under basic conditions, this difluoroenol intermediate displayed versatile reactivity, resulting dramatically improved enantioselectivity mild conditions. demonstrated catalytic asymmetric aldol reaction Mannich reactions with ketones or imines chiral organocatalysts, quinine-derived urea, phosphoric acid (CPA), respectively, relay catalysis strategy provides an effective platform for applying fluorination chemistry. Moreover, method features a novel 1,2-difunctionalization process via installation carbonyl motif alkyl group on two vicinal carbons, complementary protocol metal carbene gem-difunctionalization reaction.
Language: Английский
Citations
6
ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5211 - 5218
Published: March 12, 2025
The asymmetric electrophilic amination using azodicarboxylates as the N-source for construction of C–N bond has attracted much attention over past decades. However, use in situ formed nucleophilic intermediates, rather than bench-stable reagents, remains elusive and challenging. Herein, we disclose an enantioselective reaction generated alkylgold species with under a gold complex chiral quinine-derived squaramide (QN-SQA) synergetic catalysis, leading to alkylideneoxazolines nitrogen-containing tertiary carbon stereocenter good high yields enantioselectivities. Moreover, starting from same oxazoles incorporating aminomethyl group on 5-position could be obtained by Brønsted acid relay catalysis via alkylideneoxazoline species. This method offers complementary approach through interception With this strategic protocol, further synthetic applications can envisioned catalytic C–C C–X bonds.
Language: Английский
Citations
0
European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(27)
Published: May 22, 2024
Abstract Fluorinated organic compounds represent an important and growing family of active ingredients in various fields, including material science, pharmaceutical chemistry biological science. Developing efficient synthetic methods toward fluorinated have attracted much attention. In recent years, transition‐metal catalyzed reaction trifluoro diazo were a powerful convenient approach to afford trifluoromethyl‐ difluoromethyl‐substituted value. this review, the progress on transition‐metal‐catalyzed reactions involving their surrogates via trifluoromethylated carbene complex is described sequence 2,2,2‐trifluorodiazoethane as precursor, ethyl 3‐trifluoro‐2‐diazo‐propionate trifluoroethylamine hydrochloride or amines CF 3 CHN 2 surrogate well aldehydes/ketones N‐sulfonylhydrazones surrogate.
Language: Английский
Citations
3
Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(16), P. 3405 - 3416
Published: June 12, 2024
Abstract The enantioselective introduction of gem ‐difluorinated carbonyl (i. e. α , ‐difluoro carbonyl) moieties into organic structures is a synthetically valuable but highly challenging approach. During the past decades, continuous efforts have been made for developments synthetic strategies constructing C( sp 3 )−CF 2 COR chiral centers with high levels enantioselectivities. This review summarizes and discusses recent advance in construction moieties, which are organized according to reaction categories.
Language: Английский
Citations
2
Advanced Science, Journal Year: 2024, Volume and Issue: 12(2)
Published: Nov. 20, 2024
Abstract Chiral fully‐substituted allenes are synthetically significant and pivotal building blocks that can engage in diverse transformations toward a variety of bioactive molecules. The enantioselective assembly these skeletons using readily available reactants offers advantages but remains challenging. Herein, an asymmetric formal Michael‐type addition alkynyl imines with the key alkylgold intermediates derived situ from N ‐propargylamides is accomplished under gold‐complex chiral quinine‐derived squaramide (QN‐SQA) synergetic catalysis. Control experiments density functional theory (DFT) calculations indicated this cascade reaction involves Mannich‐type stepwise [3,3]‐σ rearrangement sequence, leading to fully substituted α‐amino allenoates, which elusive take multi‐step prepare other methods, high yields excellent enantioselectivity.
Language: Английский
Citations
2
Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 4702 - 4707
Published: Jan. 1, 2024
An asymmetric difluoroalkylation using α,α-difluoroenol as the key synthon has been disclosed, providing oxindoles containing a chiral quaternary carbon center in generally good yields and with excellent stereoselectivities.
Language: Английский
Citations
0