Asymmetric Assemblies of 1,3-Dienes, Sulfuric Diamide, and Aldehydes to Access 1,3-Diamines through Relay Amine/Palladium Catalysis

Lu, Jian-Bin; Liang, Shu‐Yuan; Gui, Wu-Tao; Chen, Zhichao; Du, Wei; Chen, Ying‐Chun

doi:10.1021/acs.orglett.2c03762

Cited by 9 publications

(5 citation statements)

References 36 publications

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“…In addition, the resultant π-allylpalladium intermediates INT5 , generated from the initial vinylogous addition of the η 2 -Pd(0)–1,3-diene complexes to imines, could be intramolecularly captured by a nucleophilic group preinstalled into the imines, thus furnishing an array of valuable chromanes 8 and 1,3-diamine derivatives 10 in good to excellent yields with outstanding enantio- and diastereoselectivity (Scheme b) . Moreover, the labile N ′-unsubstituted analogues of sulfonylimines 9 could be generated in situ from the condensation of sulfuric diamide 11 and aldehydes 12 under the catalysis of pyrrolidine, thus providing chiral 1,3-diamines 13 and even incorporating a tetrasubstituted stereogenic center via relay Pd(0) catalysis in a step- and atom-economical manner (Scheme c) . Besides imines, activated ketones were also applicable as reliable electrophilic partners for HOMO-raised Pd(0)–1,3-diene complexes.…”

Section: Asymmetric Reactions Of Electron-neutral 13-dienes Via Palla...mentioning

confidence: 99%

“…12 Moreover, the labile N′-unsubstituted analogues of sulfonylimines 9 could be generated in situ from the condensation of sulfuric diamide 11 and aldehydes 12 under the catalysis of pyrrolidine, thus providing chiral 1,3-diamines 13 and even incorporating a tetrasubstituted stereogenic center via relay Pd(0) catalysis in a step-and atom-economical manner (Scheme 5c). 15 Besides imines, activated ketones were also applicable as reliable electrophilic partners for HOMO-raised Pd(0)−1,3-diene complexes. As outlined in Scheme 5d, the αcarbonyl group of α-ketoamides 14 could be attacked by 1,3dienes in the presence of Pd(0) and bifunctional ligand L3, thus furnishing enantioenriched 3,5-cis-difunctionalized γ-lactams 15 after subsequent intramolecular allylic amination.…”

Section: 2mentioning

confidence: 99%

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Palladium(0) π-Lewis Base Catalysis: Concept and Development

Chen,

Ouyang,

et al. 2024

J. Am. Chem. Soc.

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The development of a new catalytic strategy plays a vital role in modern organic chemistry since it permits bond formation in an unprecedented and more efficient manner. Although the application of preformed metal complexes as π-baseactivated reagents have enabled diverse transformations elegantly, the concept and strategy by directly utilizing transition metals as efficient π-Lewis base catalysts remain underdeveloped, especially in the field of asymmetric catalysis. Here, we outline our perspective on the discovery of palladium(0) as an efficient π-Lewis base catalyst, which is capable of increasing the highest occupied molecular orbital (HOMO) energy of both electron-neutral and electron-deficient 1,3-dienes and 1,3-enynes upon flexible η 2complexes formed in situ and resultant π-backdonation. Thus, fruitful carbon−carbon-forming reactions with diverse electrophiles can be achieved enantioselectively in a vinylogous addition pattern, which is conceptually different from the classical oxidative cyclization mechanism. Emphasis will be given to the concept and mechanism elucidation, catalytic features, and reaction design together with perspective on the further development of this emerging field.

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Section: Asymmetric Reactions Of Electron-neutral 13-dienes Via Palla...mentioning

confidence: 99%

Section: 2mentioning

confidence: 99%

Palladium(0) π-Lewis Base Catalysis: Concept and Development

Chen,

Ouyang,

et al. 2024

J. Am. Chem. Soc.

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“…More recently, Chen and co-workers described a Pd−BIBOPcatalyzed asymmetric multicomponent cyclization reaction between 1,3-dienes, sulfuric diamide, and aldehydes. 104 This one-pot, three-component reaction featured atom economy and operational simplicity, providing an efficient and straightforward access to valuable 1,3-diamines incorporating quaternary and tertiary stereogenic centers with moderate to good enantioselectivity (Scheme 51). Importantly, the bisphosphorus DI-BIDIME with suitable steric hindrance was critical to obtain good results, as WingPhos showed moderate enantioselectivity and yield.…”

Section: P-chiral Dihydrobeznooxaphosphole Ligands For Asymmetric Cyc...mentioning

confidence: 99%

Catalysis and Synthesis Enabled by P-Chiral Dihydrobenzooxaphosphole Ligands

Cao,

He,

Tang

2024

Org. Process Res. Dev.

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P-Chiral phosphorus ligands received little attention in organic chemistry until Knowles made his landmark contribution in asymmetric hydrogenation by developing the P-chiral ligands CAMP and DIPAMP. The development of P-chiral phosphorus ligands accelerated in the end of the last century with the advent of some highly efficient and renowned ligands for asymmetric hydrogenation, including BisP*, TangPhos, QuinoxP*, DuanPhos, et al. However, most reported ligands were airsensitive, difficult to make, or lacked structural modularity, hampering their availability and applicability. The development of sterically and electronically tunable P-chiral phosphorus ligands is particularly desirable. Over the past decade, a family of sterically hindered, electron-rich, structurally tunable, and air-stable P-chiral dihydrobenzooxaphosphole ligands emerged that proved to be efficient and versatile for various asymmetric transformations. The last 5 years witnessed an increasing number of studies related to these ligands with the discovery of their unprecedented catalytic properties in various transformations. This review highlights the unique properties of P-chiral dihydrobenzooxaphosphole ligands in catalysis and their applications in the synthesis of natural products and therapeutic agents.

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“…Recently, Ying-Chun Chen, Zhi-Chao Chen, and co-workers developed a relay catalytic protocol for the synthesis of optically active 1,3-diamine derivatives by the one-pot, threecomponent reaction of 3-substituted 1,3-dienes, sulfuric diamide, and aldehydes. 636 The reaction was efficiently conducted with the combined use of pyrrolidine and the [Pd(allyl)Cl] 2 −2,6-(MeO) 2 C 6 H 3 −BIBOP catalyst, delivering six-membered 1,3-diamine derivatives 180 with quaternary and tertiary stereogenic centers in synthetically satisfactory yields and enantioselectivities (Scheme 201). It is noted that the products could be deprotected by the reaction with 1,3diaminopropane, leading to the corresponding free 1,3diamines without decrease of the enantiomeric excesses.…”

Section: C−n Bond-formingmentioning

confidence: 99%

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Imamoto

2024

Chem. Rev.

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Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality ligands and P-stereogenic phosphorus ligands. Most of the reported ligands belong to the former class. Privileged ones such as BINAP and DuPhos are frequently employed in a wide range of catalytic asymmetric transformations. In contrast, the latter class of P-stereogenic phosphorus ligands has remained a small family for many years mainly because of their synthetic difficulty. The late 1990s saw the emergence of novel P-stereogenic phosphorus ligands with their superior enantioinduction ability in Rh-catalyzed asymmetric hydrogenation reactions. Since then, numerous P-stereogenic phosphorus ligands have been synthesized and used in catalytic asymmetric reactions. This Review summarizes P-stereogenic phosphorus ligands reported thus far, including their stereochemical and electronic properties that afford high to excellent enantioselectivities. Examples of reactions that use this class of ligands are described together with their applications in the construction of key intermediates for the synthesis of optically active natural products and therapeutic agents. The literature covered dates back to 1968 up until December 2023, centering on studies published in the late 1990s and later years.

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Asymmetric Assemblies of 1,3-Dienes, Sulfuric Diamide, and Aldehydes to Access 1,3-Diamines through Relay Amine/Palladium Catalysis

Cited by 9 publications

References 36 publications

Palladium(0) π-Lewis Base Catalysis: Concept and Development

Palladium(0) π-Lewis Base Catalysis: Concept and Development

Catalysis and Synthesis Enabled by P-Chiral Dihydrobenzooxaphosphole Ligands

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

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