Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones DOI
Xiaolin Li,

Jiang-Lian Deng,

Jian Long

и другие.

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Окт. 12, 2024

Abstract Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel‐catalyzed asymmetric syn ‐hydrometalative 4‐ exo ‐ trig cyclization 1,4‐alkynones to synthesize alkenyl cyclobutanols with tetrasubstituted stereocenter. This strategy features broad substrate scope, delivering variety trifluoromethyl‐containing rigid (spiro)carbocycle skeletons in good yields high enantioselectivities (up 84 % yield 98.5 : 1.5 er). The utility is demonstrated through stereospecific transformations into fused spiro molecules. Experimental computational mechanistic studies indicate that the reaction initiated by an active Ni−H species, carbonyl‐directed hydrometalation as key regioselective control. catalytic method provides general solution hydrofunctionalization alkynes represents efficient pattern assembling highly strained enantioenriched bioisosteres.

Язык: Английский

Enantioselective Synthesis of Axially Chiral Alkylidenecycloalkanes via Copper-Catalyzed Functionalization of Acyl Allenols DOI

Baihui Gong,

Qing‐Bin Lu,

R. Li-jiun Sun

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2351 - 2358

Опубликована: Янв. 24, 2025

Язык: Английский

Процитировано

3
Cobalt-Catalyzed Diastereo- and Enantioselective Carbon–Carbon Bond Forming Reactions of Cyclobutenes DOI

Zhikun Liang,

Lei Wang, Yu Wang

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(6), С. 3588 - 3598

Опубликована: Фев. 3, 2023

Catalytic enantioselective functionalization of cyclobutenes constitutes a general and modular strategy for construction enantioenriched complex cyclobutanes bearing multiple stereogenic centers, as chiral four-membered rings are common motifs in biologically active molecules versatile intermediates organic synthesis. However, synthesis through such remained significantly limited. Herein, we report series unprecedented cobalt-catalyzed carbon-carbon bond forming reactions that initiated carbometalation. The protocols feature diastereo- introduction allyl, alkynyl, functionalized alkyl groups. Mechanistic studies indicated an unusual 1,3-cobalt migration subsequent β-carbon elimination cascade process occurred the allyl addition. These new discoveries established elementary cobalt catalysis extension diversity nucleophiles transformations cyclobutenes.

Язык: Английский

Процитировано

32
IronIII-catalyzed asymmetric inverse-electron-demand hetero-Diels–Alder reaction of dioxopyrrolidines with simple olefins DOI Creative Commons

Tangyu Zhan,

Liang Zhou, Yuqiao Zhou

и другие.

Chemical Science, Год журнала: 2024, Номер 15(13), С. 4797 - 4803

Опубликована: Янв. 1, 2024

A highly enantioselective [4 + 2] cycloaddition of a number simple olefins with cyclic hetero-diene dioxopyrrolidines is realized by chiral iron( iii )/ N , ′-dioxide complex catalyst.

Язык: Английский

Процитировано

11
Lewis Acid-Promoted [2 + 2] Cycloadditions of Allenes and Ketenes: Versatile Methods for Natural Product Synthesis DOI
Renyu Guo, M. Kevin Brown

Accounts of Chemical Research, Год журнала: 2023, Номер 56(16), С. 2253 - 2264

Опубликована: Авг. 4, 2023

ConspectusCycloaddition reactions are an effective method to quickly build molecular complexity. As predicted by the Woodward–Hoffmann rules, concerted cycloadditions with alkenes allow for constructions of all possible stereoisomers product use either Z or E geometry. While this feature is widely used in, example, [4 + 2] cycloadditions, translation [2 challenging because often stepwise and therefore stereoconvergent nature these processes. Over past decade, our lab has explored Lewis acid-promoted electron-deficient allenes ketenes alkenes. The concerted, asynchronous synthesis various cyclobutanes control stereochemistry.Our developed first examples ketene–alkene cycloadditions. Compared traditional thermal conditions, conditions have several advantages, such as increased reactivity, yield, improved diastereoselectivity, and, certain cases, inverse diastereoselectivity. Detailed mechanistic studies revealed that diastereoselectivity was controlled size substituent barrier a deconjugation event. However, required stoichiometric amounts EtAlCl2 inhibition, which led us investigate catalytic enantioselective allenoates Through chiral oxazaborolidines, broad range can be prepared enantioselectivity. Mechanistic experiments, including 2D-labled Hammett analysis, illuminate likely transition state models Additional development acid-catalyzed intramolecular stereoselective allenic ketones/esters alkenes.The methods we been instrumental in families natural products. Specifically, one key lactone motif (±)-gracilioether F constructed cycloaddition subsequent regioselective Baeyer–Villiger oxidation sequence. Enantioselective allenoate–alkene allowed (−)-hebelophyllene E. Another attempt applying (+)-[5]-ladderanoic acid failed deliver desired cyclobutane unexpected rearrangement. later assembled carboboration/Zweifel olefination process. Finally, ketones applied syntheses (−)-[3]-ladderanol, (+)-hippolide J, (−)-cajanusine.

Язык: Английский

Процитировано

20
Evans’ Chiral Auxiliary‐Based Asymmetric Synthetic Methodology and Its Modern Extensions DOI
Ling‐Yan Chen, Pei‐Qiang Huang

European Journal of Organic Chemistry, Год журнала: 2023, Номер 27(4)

Опубликована: Ноя. 21, 2023

Abstract Although the asymmetric catalysis has made a spurt of progress, use chiral auxiliaries remains crucial in synthesis due to both reliability and versatility methods, predictability stereochemistry reactions. Up date, Evans’ non‐racemic oxazolidinone‐based synthetic methodology is still widely used synthesis. More importantly, Evans turned out be fruitful source inspiration for development related methodologies. However, although reviews on application organic medicinal chemistry continually appear literature, comprehensive review dedicating extensions elusive. In this review, we summarize methodology, which cover: (1) modification oxazolidinone auxiliaries; (2) extension aldol reaction from syn ‐aldol other diastereomeric adducts; (3) types; (4) imide‐type substrates N ‐alkenyl, ‐allenenyl ‐alkynyl oxazolidinones; (5) achiral catalysis; (6) catalytic transformation products; (7) straightforward transformations products classes compounds than carboxylic acids, esters, alcohols, Weinreb amides.

Язык: Английский

Процитировано

13
Pd-catalyzed enantioselective synthesis of axially chiral alkylidene cycloalkanes DOI Creative Commons

Bing-Ru Shao,

Wenfeng Jiang,

Chao Zheng

и другие.

Chem Catalysis, Год журнала: 2023, Номер 3(7), С. 100697 - 100697

Опубликована: Июль 1, 2023

Язык: Английский

Процитировано

11
Stable Axially Chiral Cyclohexylidenes from Catalytic Asymmetric Knoevenagel Condensation DOI

Meijia Ying,

Kaixuan Wang,

Wenjun Yan

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(39)

Опубликована: Май 7, 2024

Axially chiral cycloalkylidenes are interesting but less developed axially molecules. Here, a bispidine-based amine catalytic system was to promote efficiently the asymmetric Knoevenagel condensation of N-protected oxindoles and benzofuranones with 4-substituted cyclohexanones. A variety alkylidenecycloalkanes stable axial chirality were obtained in good yields fairly er (enantiomeric ratio). Based on absolute configuration determination product DFT calculations, possible mechanism stereoselective induction proposed.

Язык: Английский

Процитировано

4
Enantioselective Reduction of Cyclobutenones Using Ene‐Reductases DOI Creative Commons
Tomohiro Yasukawa,

Pierre Gilles,

Juliette Martin

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(15), С. 3257 - 3261

Опубликована: Июнь 3, 2024

Abstract Enantioselective reduction of cyclobutenones to optically active cyclobutanones has been achieved by using whole‐cell overexpressing Seqenzym ene‐reductases (EREDs). By these enzymes, trans ‐cyclobutanones were isolated in good yields and with enantiomeric excesses up 99%.

Язык: Английский

Процитировано

4
Cu-catalyzed enantioselective assembly of axially chiral allylic boronates DOI
Shuai Wang, Jianbo Liu,

Wenyue Ma

и другие.

Science China Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 25, 2024

Язык: Английский

Процитировано

4
Concerted Enantioselective [2+2] Cycloaddition Reaction of Imines Mediated by a Magnesium Catalyst DOI
Linqing Wang,

Feiyun Gao,

Xiaoyong Zhang

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 145(1), С. 610 - 625

Опубликована: Дек. 20, 2022

Enantioselective [2 + 2] cyclization between an imine and a carbon–carbon double bond is versatile strategy to build chiral azetidines. However, α-branched allenoates have never been successfully applied in reactions with imines, as they always undergo Kwon's [4 annulation previous catalytic methods. Herein, simple situ generated magnesium catalyst was employed achieve the enantioselective reaction of DPP-imines for first time. Insightful experiments including KIE experiments, controlled Hammett plot analysis, 31P NMR studies initial intermediates indicate that current most likely involves asynchronous concerted transition state. Further mechanistic investigations by combining kinetic studies, ESI coordination complexes, on rates under different loading amounts provided details this allenoates. This new approach synthesis various aza-heterocycles, key intermediate lipid-lowering agent Ezetimibe.

Язык: Английский

Процитировано

15