Application of sSPhos as a Chiral Ligand for Palladium-Catalyzed Asymmetric Allylic Alkylation DOI Creative Commons

Philip J. Docherty,

Max Kadarauch,

Nisha Mistry

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 26(14), P. 2862 - 2866

Published: Dec. 26, 2023

Palladium-catalyzed asymmetric allylic alkylation is a versatile method for C–C bond formation. Many established classes of chiral ligands can perform reactions enantioselectively, but identification new ligand remains important future development the field. We demonstrate that enantiopure sSPhos, bifunctional monophosphine ligand, when used as its tetrabutyl ammonium salt, highly effective benchmark Pd-catalyzed reaction. explore scope and limitations experiments to probe origin selectivity. In contrast with previously explored using it appears steric bulk around sulfonate group responsible high enantioselectivity in this case, rather than attractive noncovalent interactions.

Language: Английский

Synergistic Dual Catalysis in Stereodivergent Synthesis DOI
Liang Wei, Cong Fu,

Zuo-Fei Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 3812 - 3844

Published: Feb. 23, 2024

Chiral skeletons with multiple stereogenic centers widely reside in nature and drugs, their relative absolute configuration often determine physiological or pharmacological properties. Stereodivergent synthesis of chiral molecules is not only great significance, but also highly challenging since the formation one diastereomers inherently preferred most asymmetric reactions. dual catalysis, introduced 2013 by Carreira group, perfectly catered to all requirements for full stereoselectivity control given reactions two catalysts are utilized a synergistic way act independently, has now been arguably efficient strategy realize stereodivergent synthesis. This comprehensive review presents an overview development enabled catalysis past ten years, providing readers fundamental attributes as well ability, scope, mechanism, limitations this strategy.

Language: Английский

Citations

33
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

2
Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis DOI Creative Commons

Chang You,

Mingying Shi,

Xueling Mi

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 22, 2023

We herein describe an asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes with 1,3-enynes. A synergistic chiral primary amine/Pd catalyst was identified to facilitate the utilization 1,3-enynes as atom-economic achiral allene precursors. The catalysis enables construction all-carbon quaternary centers-tethered allenes bearing non-adjacent 1,3-axial central stereogenic centers in high level diastereo- enantio-selectivity. By switching configurations ligands aminocatalysts, diastereodivergence can be achieved any four diastereoisomers accessed enantio- selectivity.

Language: Английский

Citations

27
Synergistic Palladium/Copper‐Catalyzed 1,4‐Difunctionalization of 1,3‐Dienes for Stereodivergent Construction of 1,5‐Nonadjacent Stereocenters DOI
Hongfa Wang, Ruiyuan Zhang, Weiwei Zi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 21, 2024

Abstract The construction of two distal stereocenters through a single catalytic process is great interest in organic synthesis. While there are some successful reports regarding stereodivergent preparation 1,3‐ or 1,4‐stereocenters, the more challenged 1,5‐nonadjacent have never been achieved fashion. Herein we describe synergistic palladium/copper catalysis for 1,4‐difunctionalization reactions 1,3‐dienes, providing access to quaternary stereocenters. Because each catalysts separately controlled one newly formed stereocenters, synthesis all four diastereomers products could readily be simply by choosing an appropriate combination chiral catalysts. Experimental and computational studies supported mechanism involving Heck/Tsuji–Trost cascade reaction, origins stereoselectivity were elucidated.

Language: Английский

Citations

14
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

11
Asymmetric phase-transfer catalysis DOI
Hyo‐Jun Lee, Keiji Maruoka

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(11), P. 851 - 869

Published: Oct. 9, 2024

Language: Английский

Citations

10
Photoinduced Pd-Catalyzed Formal Asymmetric Allylic Substitution of Piperidine Scaffolds DOI

Weidong Lu,

Zhilin Liu,

Zi‐Hao Liao

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4384 - 4393

Published: Feb. 26, 2025

Language: Английский

Citations

1
Diastereodivergent Catalysis DOI Creative Commons
Daniel Moser,

Tanno A. Schmidt,

Christof Sparr

et al.

JACS Au, Journal Year: 2023, Volume and Issue: 3(10), P. 2612 - 2630

Published: Sept. 26, 2023

Alongside enantioselective catalysis, synthetic chemists are often confronted by the challenge of achieving catalyst control over relative configuration to stereodivergently access desired diastereomers. Typically, these approaches iteratively or simultaneously multiple stereogenic units for which dual catalytic methods comprising sequential, relay, and synergistic catalysis emerged as particularly efficient strategies. In this Perspective, benefits challenges catalyst-controlled diastereodivergence in construction carbon stereocenters discussed on basis illustrative examples. The concepts then transferred diastereodivergent atropisomeric systems with twofold higher-order stereogenicity well E- Z-configured alkenes.

Language: Английский

Citations

21
Enantio- and diastereodivergent synthesis of fused indolizines enabled by synergistic Cu/Ir catalysis DOI Creative Commons

Bing‐Ke Zhu,

Hui Xu,

Lu Xiao

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(15), P. 4134 - 4142

Published: Jan. 1, 2023

Highly selective assembly of 2,3-fused indolizines was achieved via a cascade allylation/Friedel–Crafts type reaction with Cu/Ir catalysis. This protocol furnishes stereodivergent synthesis chiral bearing three stereogenic centers excellent results.

Language: Английский

Citations

20
Palladium-Catalyzed Asymmetric Hydrofunctionalizations of Conjugated Dienes DOI Open Access
Yuchao Wang, Jin‐Biao Liu, Zhi‐Tao He

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(8), P. 2614 - 2614

Published: Jan. 1, 2023

Because of the broad substrate availability, high atom economy and efficient stereocontrol, palladium-catalzyed asymmetric hydrofunctionalizations conjugated dienes have emerged as an route to construct enantioenriched allylic motifs, including C-C, C-N, C-S, C-P, C-Si C-O bonds.The development, advance mechanistic features this area in past decades are summarized.Based on types stereogenic centers constructed via strategy, review is divided into six parts, hydroalkylation, hydroamination, hydrophosphinylation, hydrosulfonylation, hydrosilylation hydroalkoxylation.

Language: Английский

Citations

18