Enantioselective Heck/Tsuji−Trost Reaction of Flexible Vinylic Halides with 1,3-Dienes DOI Creative Commons
Junliang Zhang, Li‐Zhi Zhang, Peichao Zhang

et al.

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 16, 2024

Abstract The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress relative rigid skeleton substrates, the implementation of asymmetric cascades highly flexible haloalkene substrates remains challenging and long-standing goal. Here we report an efficient tandem Heck/Tsuji−Trost reaction vinylic halides with 1,3-dienes enabled by palladium catalysis. A variety functional cyclic isoprenoids, which are key structural motifs numerous natural products family, were delivered good yields excellent regio-, diastereo- enantioselectivity. Specifically, Heck insertion stereodetermining step to form ƞ3 π-allyl complex situ trapping nucleophiles enable Heck/etherification formal (4+2) cycloaddition manner. Engineering Sadphos bearing androgynous non-C2-symmetric chiral sulfinamide phosphine ligands vital component achieving catalytic reactivity This strategy offers general, modular divergent platform rapidly upgrading feedstock dienes various value-added molecules is expected inspire development other Heck/cross-couplings.

Language: Английский

Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes DOI Creative Commons

Li-Zhi Zhang,

Peichao Zhang, Qian Wang

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 22, 2025

Abstract The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress relative rigid skeleton substrates, the implementation of asymmetric cascades highly flexible haloalkene substrates remains challenging and long-standing goal. Here we report an efficient Heck/Tsuji−Trost reaction vinylic halides with 1,3-dienes enabled by palladium catalysis. Specifically, Heck insertion stereodetermining step to form ƞ 3 allyl complex situ trapping nucleophiles enable Heck/etherification formal (4 + 2) cycloaddition manner. Engineering Sadphos bearing androgynous non-C 2 -symmetric chiral sulfinamide phosphine ligands are vital component achieving excellent catalytic reactivity enantioselectivity. This strategy offers general, modular divergent platform rapidly upgrading feedstock dienes various value-added molecules is expected inspire development other Heck/cross-couplings.

Language: Английский

Citations

0
Nickel‐Catalyzed Asymmetric Reductive 1,4‐ and 1,5‐Dicarbofunctionalization† DOI Open Access
Yutong Xiang,

Chang Zhang,

Chuan Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 8, 2025

Comprehensive Summary Herein, we present the first examples of asymmetric reductive 1,4‐dicarbofunctionalization 1,3‐dienes and 1,5‐dicarbofunctionalization vinylcyclopropanes, which proceed under catalysis a chiral nickel/bis‐imidazoline complex using alkyl halides aryl iodides or alkenyl bromides as electrophilic coupling partners. In these highly enantioselective transformations operating in radical relay mechanism, C(sp 3 )‐ 2 )‐type carbo‐moieties are respectively installed on terminal internal position with newly formed olefinic unit high E ‐selectivity.

Language: Английский

Citations

0
Trifluoromethyl Group (CF3) Induced Regioselective Larock Indole Synthesis from Unsymmetric β-CF3-1,3-enynes DOI

Yan‐Hua Qiu,

Peng-Xiang Ma,

Wen‐Hao Shao

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

The indole skeleton exists widely in natural products, pharmaceuticals, and materials. We disclose here a trifluoromethyl group induced regioselective Larock synthetic method from unsymmetric 2-CF3-1,3-enynes. presence of is determinable for the regioselectivity. Once CF3 was replaced with methyl or phenyl group, ratio 1:1 to 1:1.4 isomers were obtained. This strategy features good regioselectivity, broad substrate scope, high functional tolerance. protocol reported offers an alternative solution rare 3,4-functionalization products further transformed show distinctive reactivity hydroboration–oxidation hydro-bromination.

Language: Английский

Citations

0
SadPhos Library: A Comprehensive Resource for Exploring Chiral Ligand Chemical Space DOI
Shuang Yu

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Abstract Traditionally, the discovery of ligands for organic reactions has relied heavily on intuition and experience chemists, leading to a trial‐and‐error process that is both time‐consuming inherently biased. The rise data science now offers more systematic efficient approach exploring chemical spaces, moving beyond heuristic constraints conventional ligand design enabling data‐driven, predictive method. In this study, we introduce “SadPhos Library”, comprehensive collection 890 reported chiral sulfinamide phosphine ligands, use physical descriptors systematically map their space. By examining small dataset known active demonstrate how SadPhos library can help identify key properties associated with performance thus streamline optimization. Furthermore, employing dimensionality reduction clustering techniques, pinpoint representative subset facilitates targeted exploration diverse landscape.

Language: Английский

Citations

0
Palladium-catalyzed allylation and carbonylation: access to allylhydrazones and allyl acylhydrazones DOI

Qianqian Liang,

Yan Cai,

Wenjun Jiang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(12), P. 1638 - 1641

Published: Jan. 1, 2024

A practical one-pot catalytic tandem multicomponent allylation condensation carbonylation to construct allylhydrazones and allyl acylhydrazones with high atom economy, water as a coproduct excellent regioselectivity in reactions.

Language: Английский

Citations

3
Palladium-catalyzed selective C–C bond cleavage of keto-vinylidenecyclopropanes: construction of structurally rich dihydrofurans and tetrahydrofurans DOI Creative Commons
Chao Ning, Ziqi Yu, Min Shi

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(24), P. 9192 - 9200

Published: Jan. 1, 2024

A series of bicyclic products containing dihydrofuran and tetrahydrofuran skeletons were obtained by divergent palladium-catalyzed selective C–C bond cleavage keto-VDCPs. The reaction mechanism was also investigated systematically.

Language: Английский

Citations

3
Enantioselective Aminosilylation of Alkenes by Palladium/Ming‐Phos‐Catalyzed Tandem Narasaka–Heck/Silylation Reaction DOI Creative Commons

Kangning Cao,

Jie Han, Wenshao Ye

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: July 5, 2024

A Pd-catalyzed enantioselective aminosilylation of alkenes via tandem Aza-Heck/silylation reaction under Pd/Sadphos catalysis is disclosed. wide array oxime esters and silicon reagents are tolerated, furnishing the chiral pyrrolines bearing one quaternary or two contiguous stereocenters in good yield with high enantioselectivity. Not only terminal but also tri-substituented internal successfully participate reaction, delivering vicinal complete diastereoselectivity DFT study conducted to probe pathway origin enantioselectivity, which revealed that stereoinduction arises from weak interaction between aromatic ring substrate fragment naphthyl group ligand.

Language: Английский

Citations

3
Lewis/Brønsted acid-mediated cyclization/amidation of 1,6-enynes with nitriles: access to 3-enamide substituted dihydrobenzofurans DOI
Zan Chen, Wenting Huang,

Yu Su

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(30), P. 4523 - 4526

Published: Jan. 1, 2023

A novel Lewis- and Brønsted-acid mediated electrophilic addition cyclization/amidation reaction of 1,6-enynes with nitriles to synthesize 3-enamide-substituted dihydrobenzofurans has been developed. The transformation involves the a Brønsted acid as reagent enynes, followed by intramolecular cyclization form cationic intermediates, termination nitrile nucleophile. main features include high atom economy chemoselectivity, well construction C-C/C-N bonds in one step.

Language: Английский

Citations

6
Dienes as Versatile Substrates for Transition Metal‐Catalyzed Reactions DOI
Amanda M. Canfield, Dasha Rodina, Shauna M. Paradine

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(20)

Published: March 4, 2024

Abstract Dienes have been of great interest to synthetic chemists as valuable substrates due their abundance and ease synthesis. Their unique stereoelectronic properties enable broad reactivity with a wide range transition metals construct molecular complexity facilitating synthesis biologically active compounds. In addition, structural diene variation can result in substrate‐controlled reactions, providing mechanistic insights into selectivity patterns. The last decade has seen wealth new methodologies involving through the power metal catalysis. This review summarizes recent advances remaining opportunities for metal‐catalyzed transformations dienes.

Language: Английский

Citations

1
Stereoselective Synthesis of Highly Substituted 1,3-Dienes through Dual 1,3-Sulfur Rearrangement of Dithianes with Alkynylsilanes DOI
Ruipeng Li, Xi Chen, Xiang‐Rong Xu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 26(3), P. 581 - 585

Published: Dec. 5, 2023

Herein, we report a C3 and C1 coupling approach between vinyl 1,3-dithiane derivatives alkynylsilanes for the construction of highly substituted conjugated dienes. Through regioselective dual 1,3-sulfur migration process, this method enabled synthesis wide range (E)-1,3-dienes stereoselectively in moderate to high yields, which provided one alternative way synthesize corresponding dienones.

Language: Английский

Citations

3