Enantioselective Total Synthesis of [3]‐Ladderanol through Late‐Stage Organocatalytic Desymmetrization** DOI
Sayan Ray, Subhajit Mondal, Santanu Mukherjee

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 25, 2022

Ladderane phospholipids, with their unusual ladder-like arrangement of concatenated cyclobutane rings, represent an architecturally unique class natural products. However, despite fascinating structure and other necessary impetus, only a few synthetic studies these molecules have been reported so far. We now devised concise total synthesis [3]-ladderanol, component ladderane using organocatalytic enantioselective desymmetrizing formal C(sp2 )-H alkylation. Our strategy rests on the late-stage introduction chirality, thus allowing facile access to both enantiomers [3]-ladderanol as well analogue. This is first time desymmetrization applied [3]-ladderanol. The scope this alkylation meso-cyclobutane-fused cyclohexenediones also presented.

Language: Английский

Remote Enantioselective Desymmetrization of 9,9-Disubstituted 9,10-Dihydroacridines through Asymmetric Aromatic Aminations DOI

Dekun Zhang,

Yingbo Shao,

Wansen Xie

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(23), P. 14609 - 14618

Published: Nov. 15, 2022

Enantio-enriched 9,10-dihydroacridines are useful chiral N-heterocycles in many aspects; however, their asymmetric catalytic synthesis is rather challenging, as the stereocenter remote to functional group. Herein, we disclose an efficient enantioselective desymmetrization protocol through aromatic aminations enabled by a new type of spirocyclic phosphoric acid (CPA) catalyst, which gave access wide range dihydroacridines bearing 9,9-disubstitutions with extremely broad scope (compatible both aryl,alkyl- and dialkyl-substitutions) excellent enantioselectivities (up >99% ee). In addition, this method was also applicable construction stereogenic silicon center kinetic resolution unsymmetrical dihydroacridine derivatives. Density theory calculations were performed elucidate origin regio- enantioselectivity these reactions, arose from skeletons bulky polyaromatic substitutions CPA catalyst.

Language: Английский

Citations

18
Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis DOI Creative Commons
Harry Adams,

Max Kadarauch,

Nicholas J. Hodson

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside variety other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these catalyst designs that also incorporate reactive transition metal. In isolation, single interaction exhibits low directionality, but many successful systems they exist additional which provide high degree organization at the selectivity-determining state. Even situations with key interaction, directionality is not always detrimental, and even be advantageous, conferring generality catalyst. This Review explores approaches utilize control selectivity metal It divided into halves: first, occurs outer sphere complex, using ligand or bound an anion; second, bears formal charge, associated counterion.

Language: Английский

Citations

0
Palladium-catalyzed enantioselective β-hydride elimination for the construction of remote stereocenters DOI Creative Commons
Shaozi Sun, Shengnan Sun, Weiwei Zi

et al.

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

Published: March 5, 2025

The β-H elimination is a crucial elementary step in transition-metal catalysis, but controlling the stereochemistry of this process has been underdeveloped. limited works reported so far have only focused on creating axial chirality allenes, and no report able to build central using asymmetric elimination. In study, we Trost ligand-enabled enantioselective desymmetric reaction from π-allyl-Pd. This transformation provides rapid access cyclohexenes bearing C4-remoted stereocenter, total synthesis (-)-oleuropeic acid (-)-7-hydroxyterpineol demonstrated. Computational studies shown that rate-determining step, non-covalent interactions between amide moiety ligand benzene cyclohexane moieties substrate play key role stereocontrol during

Language: Английский

Citations

0
Recent advances in the synthesis and transformations of sulfinate esters DOI Creative Commons
Suguru Yoshida

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Recent sulfinate esters chemistry is summarized in this feature article. Efficient methods to synthesize diverse from readily available starting materials and various modern transformations of are introduced.

Language: Английский

Citations

0
Enantioselective Total Synthesis of [3]‐Ladderanol through Late‐Stage Organocatalytic Desymmetrization** DOI
Sayan Ray, Subhajit Mondal, Santanu Mukherjee

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 25, 2022

Ladderane phospholipids, with their unusual ladder-like arrangement of concatenated cyclobutane rings, represent an architecturally unique class natural products. However, despite fascinating structure and other necessary impetus, only a few synthetic studies these molecules have been reported so far. We now devised concise total synthesis [3]-ladderanol, component ladderane using organocatalytic enantioselective desymmetrizing formal C(sp2 )-H alkylation. Our strategy rests on the late-stage introduction chirality, thus allowing facile access to both enantiomers [3]-ladderanol as well analogue. This is first time desymmetrization applied [3]-ladderanol. The scope this alkylation meso-cyclobutane-fused cyclohexenediones also presented.

Language: Английский

Citations

16