501919-44-4

Upstream product

• 1121-66-0 2-Cyclohepten-1-one 
• 312-40-3 difluorodiphenylsilane 
• 24388-23-6 2-phenyl-4,4,5,5-tetramethyl-1,3,2-dioxoborole 
• 108-86-1 bromobenzene 
• 934-56-5 trimethyl(phenyl)stannane 
• 147068-27-7 3-phenyl-2-cyclohepten-1-one 
• 1194-18-9 cycloheptane-1,3-dione 
• 86616-78-6 3-ethoxycyclohept-2-en-1-one 
• 502-42-1 cycloheptanone 
• 98-80-6 phenylboronic acid 
• 100-58-3 phenylmagnesium bromide 
• 603-33-8 triphenylbismuthane 

Relevant academic research and scientific papers

Fine-Tuning the Bicyclo[3.3.1]nona-2,6-diene Ligands: Second Generation 4,8-Substituted Dienes for Rh-Catalyzed Asymmetric 1,4-Addition Reactions

Design and synthesis of the second generation C2-symmetric 4,8-endo,endo-bis(alkoxy) bicyclo[3.3.1]nona-2,6-diene ligands possessing additional 4,8-exo,exo substituents is reported. The 4,8-exo,exo groups provide a further element for fine-tuning of the ligand structure by enforcing conformational rigidity of the 4,8-endo,endo side chains. Such tetrasubstituted bicyclo[3.3.1]nona-2,6-dienes were employed as steering ligands in the rhodium-catalyzed arylation of cyclic enones with arylboronic acids, providing the corresponding 1,4-addition products in good to excellent yields (69–99 %) and enantioselectivities up to 99 % ee.

Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem?

The enantioselective hydrogenation of endocyclic enones has been a historical problem for homogeneous catalysis. We herein report an efficient method to reduce endocyclic enones with molecular hydrogen. Catalyzed by a rhodium/Zhaophos complex, a variety of enones with five-, six- or seven-member ring were hydrogenated with high enantioselectivity (92%—99% ee). Excellent chemo- and enantioselectivity demonstrated this method was successfully applied in the enantioselective hydrogenation of citral to produce enantio-enriched citronellal.

trans-Cyclooctenes as Chiral Ligands in Rhodium-Catalyzed Asymmetric 1,4-Additions

trans-Cyclooctenes serve as asymmetric ligands for the rhodium-catalyzed 1,4-additions of organotin reagents to enones. We demonstrate, for the first time, that these chiral olefins can provide efficient coordination spheres for asymmetric metal catalysis. As the asymmetric environment around the reaction site is constructed by the trans-cyclooctene framework, the introduction of a substituent at the allylic position further improves enantioselectivity to 93 % ee. These findings provide new chiral framework designs for the asymmetric ligands of metal catalysts.

A diastereomeric pair of sulfoxide-containing chiral MOP-type ligands: Preparation and application to rhodium-catalyzed asymmetric 1,4-addition reactions

(R,SS)-Sulfoxide-MOP (L2) and (R,RS)-sulfoxide-MOP (L3) were developed as a diastereomeric pair of sulfoxide-containing chiral MOP-type ligands. These two ligands also represent the first monosulfoxide analogues of BINAP. The chiral ligand L2 was successfully applied to the highly enantioselective rhodium-catalyzed 1,4-addition between α,β-unsaturated ketones or esters and arylboronic acids, and exhibited a broad substrate scope when the reaction was performed using 1.5 mol% Rh in cyclohexane/H2O (10:1) at 40 °C under mild basic conditions.

Chiral Bicyclic Bridgehead Phosphoramidite (Briphos) Ligands for Asymmetric Rhodium-Catalyzed 1,2- and 1,4-Addition

A complementary solution for Rh-catalyzed enantioselective 1,2- and 1,4-arylation with two structurally related chiral ligands is reported. A chiral bicyclic bridgehead phosphoramidite (briphos) ligand derived from 1-aminoindane was efficient for the 1,2-arylation of N-sulfonyl imines, while that derived from 1,2,3,4-tetrahydro-1-naphthylamine was efficient for 1,4-arylation of α,β-unsaturated cyclic ketones. For α,β-unsaturated N-tosyl ketimines, the briphos derived from 1-aminoindane was found to selectively provide γ, γ-diaryl N-tosyl enamines with high yields and stereoselectivities.

4,8-disubstituted bicyclo[3.3.1]nona-2,6-dienes as chiral ligands for rh-catalyzed asymmetric 1,4-addition reactions

C2-symmetric chiral diene ligands based on 4,8-endo,endo-disubstituted bicyclo[3.3.1]nona-2,6-diene framework have been designed and synthesized. The rhodium complexes of the dienes, which were obtained in a few straightforward steps from enantiomerically pure bicyclo[3.3.1]nonane-2,6-dione, exhibited excellent catalytic activity and high enantioselectivity (up to 96% ee) in the conjugate addition reaction of arylboronic acids to cyclic enones under mild reaction conditions with high atom efficiency. Chiral C2-symmetric 4,8-endo,endo-disubstituted bicyclo[3.3.1]nona-2,6-diene ligands were synthesized from easily available bicyclo[3.3.1]nonane-2,6-dione and utilized in the asymmetric 1,4-addition reaction of arylboronic acids to cyclic enones. The catalyst prepared in situ from ligand 4b and [RhCl(C2H4)2]2 exhibited excellent catalytic activity and high enantioselectivity (up to 96% ee) under mild reaction conditions with high atom efficiency.

Flexible C2-symmetric bis-sulfoxides as ligands in enantioselective 1,4-addition of boronic acids to electron-deficient alkenes

The application of acyclic C2-symmetric chelating bis-sulfoxide ligands in the Rh(I)-catalyzed enantioselective 1,4-addition of boronic acids to electron-deficient alkenes is reported. Among the acyclic ethane-bridged bis-sulfoxides tested, the

Expanding the C1-symmetric bicyclo[2.2.1]heptadiene ligand family: Highly enantioselective synthesis of cyclic β-aryl-substituted carbonyl compounds

The efficient preparation of highly enantioenriched cyclic β-aryl-substituted carbonyl compounds has been achieved through the Rh I-catalyzed asymmetric 1,4-addition of an array of arylboronic acids to cyclic α,β-unsaturated carbonyl compounds. In the presence of 0.1 or 0.5 mol-% of the RhI/1g complex, the products of conjugate addition were isolated in 89 to 98%ee and in good to excellent yield.

"Sulfolefin": Highly modular mixed S/Olefin ligands for enantioselective Rh-catalyzed 1,4-addition

Reported is a single high yielding step approximation to mixed olefin/sulfinamide ligands enclosing a chiral sulfur atom as the sole chiral center. The synthetic design is validated by a rapid optimization of the substituent at the sulfinyl sulfur, and by

(S)-Phenylalanine-derived chiral phosphorus-olefin ligands in rhodium-catalyzed asymmetric 1,4-addition reactions

Chiral phosphorus-olefins (S)-1, (S)-4, and (S)-5 have been designed and synthesized. These ligands were all synthesized from (S)-phenylalanine derivatives and act as phosphorus-olefin bidentate ligands to rhodium. The coordination face of the olefin can