Diastereodivergence in catalytic asymmetric conjugate addition of carbon nucleophiles DOI
Byungjun Kim,

Hooseung Lee,

In‐Sun Song

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 11, 2024

Catalytic asymmetric conjugate additions of carbon nucleophiles have emerged as a potent tool for constructing multi-stereogenic molecules with precise stereochemical control. This review explores the concept diastereodivergence in such reactions, focusing on strategies to achieve selective access diverse diastereomeric products upon carbon-carbon bond formation. Drawing from rich array examples, we delve into key approaches controlling outcome these transformations, including alteration alkene geometry, fine-tuning reaction parameters, synergistic catalysis, and isomerization adducts. Additionally, highlight iterative additions, showcasing their potential diastereodivergent synthesis methyl-branched stereocenters 1,3-relationships. By presenting concentrated overview this significant topic, aims provide valuable insights design execution stereodivergent catalytic offering new avenues advancing stereoselective structural diversity organic synthesis.

Language: Английский

Atroposelective catalysis DOI

Tanno A. Schmidt,

Valeriia Hutskalova,

Christof Sparr

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

Citations

16
Synergistic Catalysis Involving Palladium for Stereodivergent Csp3–Csp3 Coupling Reactions DOI
Hongfa Wang, Qinglong Zhang, Weiwei Zi

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 31, 2024

ConspectusTransition-metal-catalyzed coupling reactions of dienes (such as 1,3-dienes, alkoxyallenes, and aminoallenes) with carbon nucleophiles have proven to be a highly effective method for creating Csp3–Csp3 bonds. These perfect atom economy typically occur under mild reaction conditions. By using chiral metal complexes catalysts, it is possible create enantioenriched molecules bearing allylic stereocenters high enantioselectivities. However, challenges arise when bonds two vicinal are constructed through this type reaction. Due the inherent diastereoselectivities, only kinetically favored diastereoisomers (either syn- or anti-product) usually obtained transition-metal catalyst system. Achieving complementary stereoisomers selectivity, which require complete control both absolute relative configurations multiple centers in single chemical transformation, impossible.Over past decade, significant advancements been made stereodivergent synthesis. Notably, iridium-related synergistic catalysis has rapidly developed alkylation reactions. these systems were limited alcohol derivatives electrophilic partners. Finding ways extend use other types crucial issue that needs addressed.In 2019, we reported first palladium-mediated system between 1,3-dienes aldimine esters. Lately, strategy successful accessing diverse substrate patterns. In Account, will summarize our laboratory's efforts developing range palladium-involved dienes. We discovered several systems, including Pd/Cu(Ag), Pd/amine, Pd/Lewis base, Pd/PTC. Additionally, dienes, such aminoallenes, serve suitable partners coupling. processes provide an efficient constructing scaffolds stereocenters. Density functional theory (DFT) calculations performed elucidate mechanism rationalize origins stereochemistry some systems. Finally, synthetic application methods demonstrated concise total synthesis number natural products bioactive molecules. It anticipated increasing chemists join research on contribute more elegant examples area. believe future development further push boundary asymmetric find innovative applications soon synthesizing complex

Language: Английский

Citations

8
Stereodivergent Construction of 3,3′-Disubstituted Oxindoles via One-Pot Sequential Allylation/Alkylation and Its Application to the Total Synthesis of Trigolute B and D DOI

Bin Qing,

Zhuang Yang, Zhenwei Wu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

The absolute and relative configurations of bioactive chiral molecules are typically relevant to their biological properties. It is thus highly important desirable construct all possible stereoisomers a lead candidate or given natural compound. Synergistic dual catalysis has been recognized as reliable synthetic strategy for variety predictable stereodivergent transformations. Despite the impressive progress made in this field, carbon-carbon bond-formation reactions involving stabilized nucleophiles remain elusive. Herein, we report an iridium- magnesium-catalyzed one-pot sequential allylic alkylation/nucleophilic alkylation cascade process synthesis four 3,3'-disubstituted oxindoles through three-component reaction. A diverse array products readily prepared with high functional group compatibility good yields excellent diastereo- enantioselectivities. Subsequently, total spirooxindole alkaloid trigolutes B D accomplished concise unified route using same set starting materials.

Language: Английский

Citations

1
Bimetallic Ru/Ru‐Catalyzed Asymmetric One‐Pot Sequential Hydrogenations for the Stereodivergent Synthesis of Chiral Lactones DOI Creative Commons

Jingli He,

Zhaodi Li,

Ruhui Li

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(23)

Published: March 21, 2024

Abstract Asymmetric sequential hydrogenations of α ‐methylene γ ‐ or δ ‐keto carboxylic acids are established in one‐pot using a bimetallic Ru/Ru catalyst system, achieving the stereodivergent synthesis all four stereoisomers both chiral and ‐lactones with two non‐vicinal carbon stereocenters high yields (up to 99%) excellent stereoselectivities >99% ee >20:1 dr). The compatibility Ru systems is investigated detail, it found that basicity reaction system plays key role hydrogenation processes. protocol can be performed on gram‐scale low loading 11000 S/C) resulting products allow for many transformations, particularly several intermediates useful preparation drugs natural products.

Language: Английский

Citations

8
Simultaneous construction of inherent and axial chirality by cobalt-catalyzed enantioselective C-H activation of calix[4]arenes DOI Creative Commons
Tong Li, Yanbo Zhang, Cong Du

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Sept. 3, 2024

Language: Английский

Citations

6
Catalytic stereodivergent and simultaneous construction of axial and point chirality DOI
Wentao Wang, Sen Zhang,

Wenxuan Lin

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3308 - 3319

Published: Jan. 1, 2024

An unprecedented ligand-enabled stereodivergent construction of both N–N axial and point chirality in a single step is reported.

Language: Английский

Citations

5
A review on solvent-controlled stereodivergent catalysis DOI Open Access
Akanksha Kumari, Anshul Jain, Nirmal K. Rana

et al.

Tetrahedron, Journal Year: 2023, Volume and Issue: 150, P. 133754 - 133754

Published: Nov. 25, 2023

Language: Английский

Citations

11
A stereodivergent multicomponent approach for the synthesis of C–N atropisomeric peptide analogues DOI Creative Commons

Natalie J. Roper,

Aaron D. G. Campbell, Paul G. Waddell

et al.

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

Published: Jan. 1, 2024

Four-component reactions at room temperature delivered C–N atropisomeric peptide analogues possessing both central and axial chirality with complete diastereocontrol. Reactions elevated selectively afforded the other diastereoisomer.

Language: Английский

Citations

3
Divergent Synthesis of Chiroptical Molecular Switches Based on 1,2-Diaxial Atropisomers DOI Creative Commons

Tian‐Jiao Han,

Qingxiang Yang, Jin‐Feng Hu

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(11), P. 4445 - 4454

Published: Oct. 14, 2024

The development of chiroptical molecular switches for chiral sensing, data communication, optical displays, logic gates, and asymmetric catalysis is currently a vibrant frontier science technology. Herein, we report practical artificial dynamic system based on 1,2-diaxial atropisomer. Organocatalytic parallel kinetic resolution allows the divergent synthesis two sets stereoisomers with vicinal C-C N-N axes from same racemic single-axis substrates. By simply varying configuration single catalyst, all four are accessible. successive conduction covalent unlocking/locking thermal-isomerization processes enables sequential switching between atropisomeric states electronic circular dichroism signal reversal, providing an example multistate switches.

Language: Английский

Citations

2
Stereodivergent dual catalysis in organic synthesis DOI

Hong Sun,

Yue Ma,

Guorong Xiao

et al.

Trends in Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

Citations

2