Asymmetric 2,4-Dienylation/[4 + 2] Annulation Cascade to Construct Fused Frameworks via Auto-Tandem Palladium Catalysis

Zhu, Jian-Xiang; Pi, Fu; Sun, Teng; Huang, Wen-Yu; Gao, Lu; Chen, Zhi-Chao; Du, Wei; Chen, Ying-Chun

doi:10.1021/acs.orglett.3c01084

Cited by 7 publications

(2 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Next, we further expanded the scope of ( E )-styrylboronic acids to dienyl boronic acids (Table ). According to the literature, the active 1,3-diene motif is generally considered to be a good conversion functional group, constructing a set of cyclic systems through rapid cycloaddition reactions . After optimization of the conditions, we found that ((1 E , 3 E )-4-phenylbutane-1,3-diene-1-boronic acid 1a as a raw material was rapidly reacted with 2a to provide the target product 6a .…”

Section: Resultsmentioning

confidence: 97%

Carbene-Catalyzed Enantioselective Petasis-Like Alkenylation

Li,

Zhang,

et al. 2024

ACS Catal.

View full text Add to dashboard Cite

The N-heterocyclic carbene (NHC)-catalyzed enantioselective Petasis-like alkenylation of o-hydroxycinnamaldehydes or hydroxyl-tethered α,β-unsaturated aldehydes with styryl, dienyl, or trienyl boronic acids is disclosed. This method involves the addition of π-system-containing boronic acids to NHC-bounded α,β-unsaturated acyl azoliums and allows access to divergent assembly of β-alkenyl substituted dihydrocoumarin and γand δ-lactones. DFT calculations suggest that an unprecedented zwitterionic intermediate and 1,4-or 1,5-migration of alkenyl groups play a crucial role in the reaction. More in-depth studies of orbital and noncovalent interaction analysis provide more detailed explanations for pathways and stereoselectivity control.

show abstract

Section: Resultsmentioning

confidence: 97%

Carbene-Catalyzed Enantioselective Petasis-Like Alkenylation

Li,

Zhang,

et al. 2024

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…We further developed a palladium-catalyzed autotandem process between 2,4-dienyl carbonate 21 and ortho -functionalized activated alkene 27 . As depicted in Scheme b, a similar Tsuji–Trost reaction/Michael addition/π–σ–π isomerization/allylic alkylation sequence occurred smoothly under the catalysis of Pd 2 (dba) 3 and L9 to deliver fused and spirocyclic framework 29 in excellent yield and stereoselectivity.…”

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

confidence: 99%

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

Chen,

Ouyang,

et al. 2024

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Enantioselective Construction of Polycyclic Chromanes through Organocatalytic Sequential Quintuple Reaction via One‐Pot Step‐Wise Procedure

Wang,

Qin,

Song

et al. 2024

Chin. J. Chem.

View full text Add to dashboard Cite

Comprehensive SummaryAn efficient and highly stereoselective synthetic method to access polycyclic chromanes has been achieved through organocatalyzed one‐pot step‐wise reactions involving 2‐hydroxycinnamaldehydes, 2‐aminochalcones, and malononitrile as substrates. The reactions underwent a quintuple process by aza‐Michael/Michael/Knoevenagel/oxa‐Michael/aldol‐type reaction in sequence to give products bearing 3 new generated rings and 5 chiral centers in moderate to quantitative yields with excellent stereoselectivities. A novel retro‐reaction mechanism was discovered in the synthetic transformations of products.

show abstract

Asymmetric 2,4-Dienylation/[4 + 2] Annulation Cascade to Construct Fused Frameworks via Auto-Tandem Palladium Catalysis

Cited by 7 publications

References 31 publications

Carbene-Catalyzed Enantioselective Petasis-Like Alkenylation

Carbene-Catalyzed Enantioselective Petasis-Like Alkenylation

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

Enantioselective Construction of Polycyclic Chromanes through Organocatalytic Sequential Quintuple Reaction via One‐Pot Step‐Wise Procedure

Contact Info

Product

Resources

About