The highly enantioselective asymmetric allylic alkylation of Morita-Baylis-Hillman carbonates with bis(phenylsulfonyl)methane is presented. The reaction is simply catalyzed by cinchona alkaloid derivatives affording the final alkylated products in good yields and enantioselectivities.
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http://dx.doi.org/10.1039/c1ob06308a | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Shanghai Inst Org Chem, State Key Lab Organometallic Chem, 345 Lingling Lu, 200032, Shanghai, CHINA.
Rhodium-catalyzed regio- and enantioselective allylic arylation of racemic alkyl- and aryl- substituted allylic carbonates with arylboronic acids using commercially available BIBOP ligand is reported. This reaction proceeds at room temperature without base or other additive to deliver allylic arylation products in excellent yields, regio- and enantioselectivity (up to 95% yield, >20:1 b/l, >99% ee). Rh/BIBOP is disclosed as an efficient catalytic system for allylic substitution reaction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Dalian University of Technology, School of Chemical Engineering, No 2 Linggong Road,Ganjingzi District, 116024, Dalian, CHINA.
The Pd-catalyzed asymmetric hydrogenolysis rearrangement of allylic acetates using (s-Bu)3BHK has been described, achieving the synthesis of axially chiral alkylidene cycloalkanes with excellent enantioselectivities (up to 99% ee) and a wide substrate scope (30 examples of cyclohexanes and cyclobutanes). To the best of our knowledge, this is the first time to achieve synthesis of axially chiral olefins via asymmetric hydrogenolysis of allylic acetates. This methodology not only offers a novel synthetic pathway for non-atropisomeric axially chiral structures but also highlights the potential of asymmetric hydrogenolysis as a powerful tool in synthetic organic chemistry.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
IISER Kolkata: Indian Institute of Science Education and Research Kolkata, Department of Chemical Sciences, Mohanpur, 741246, Nadia, INDIA.
Chiral allyl amines are important structural components in natural products, pharmaceuticals, and chiral catalysts. Herein, we report a cobalt-catalyzed enantioselective reductive coupling of imines with internal alkynes to synthesize chiral allyl amines. The reaction is catalyzed by a cobalt complex derived from commercially available bisphosphine ligand utilizing zinc as the electron donor.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
The asymmetric Tsuji-Trost reaction has been extensively studied due to its importance in establishing stereogenic centers, often adjacent to an -olefin moiety in organic molecules. The generally preferential formation of chiral -olefin products is believed to result from the thermodynamically more stable -π-allylpalladium intermediate. The rapid associative π-σ-π isomerization makes it challenging to synthesize chiral -olefin products via the transient -π-allylpalladium intermediate.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
Highly stereo- and enantioselective synthesis of δ-alkyl-substituted ()-homoallylic alcohols via asymmetric allylation is developed. In the presence of a chiral phosphoric acid catalyst, allylation of aldehydes with α-substituted allylboronates provides δ-alkyl-substituted homoallylic alcohols with excellent ()-selectivities and enantioselectivities.
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