42307-60-8

Upstream product

• 873-66-5 1-propenylbenzene 
• 201230-82-2 carbon monoxide 
• 766-90-5 cis-1-phenyl-1-propylene 
• 4513-94-4 1H-pyrrole-2-carbonitrile 
• 20452-67-9 phenylethylketene 
• 2245-25-2 2-phenyl-1,2-epoxybutane 
• 90-27-7 2-Phenylbutyric acid 
• 2294-71-5 (-)-(R)-2-phenyl-butyric acid methyl ester 
• 444575-79-5 carbonic acid 1,1-dimethylethyl 1-phenyl-2-propenyl ester 
• 100-52-7 benzaldehyde 
• 7217-71-2 1-phenyl-2-propenyl acetate 
• 103-80-0 phenylacetyl chloride 
• 159213-05-5 pseudoephedrine benzeneacetamide 
• 201005-62-1 (4R,E)-4-ethyl-2-(2-phenylethenyl)-4,5-dihydro-1,3-oxazole 

Downstream Products

• 16460-75-6 (R)-2-phenyl-butan-1-ol 
• 106268-80-8 (4R,5R)-5-phenyl-1-hepten-4-ol 
• 106268-79-5 (4S,5R)-5-phenyl-1-hepten-4-ol 

Relevant academic research and scientific papers

1,1-Diborylalkyl-1-Metal Compounds, Preparation Method Thereof, and Their Applications Toward Synthesis of 1,1-Diboronate Ester Compounds

The present invention relates to a 1,1-diborylalkyl-1-metal compound including one metal group together with two identical boron groups at the sp3 carbon center, and its use. Specifically, the present invention relates to development of novel organic reactions, synthesis of functional molecules, and synthesis of new drugs by applying the novel 1,1-diboryl-1-metal substituted alkyl compounds to various molecular libraries which could not be synthesized by conventional methodologies.

Enantioselective Copper-Catalyzed Defluoroalkylation Using Arylboronate-Activated Alkyl Grignard Reagents

A copper-catalyzed system has been introduced for the enantioselective defluoroalkylation of linear 1-(trifluoromethyl)alkenes through C-F activation to synthesize various gem-difluoroalkenes as carbonyl mimics. For the first time, arylboronate-activated alkyl Grignard reagents were uncovered in this cross-coupling reaction. Mechanistic studies confirmed that the tetraorganoborate complexes generated in situ were the key reactive species for this transformation.

Generation and Application of (Diborylmethyl)zinc(II) Species: Access to Enantioenriched gem-Diborylalkanes by an Asymmetric Allylic Substitution

We report the successful generation of (diborylmethyl)zinc(II) species by transmetallation beteween isolable (diborylmethyl)lithium and zinc(II) halide (X=Br, Cl) and their application in the synthesis of enantioenriched gem-diborylalkanes bearing a stereogenic center at the β-position of the diboryl groups by an asymmetric allylic substitution reaction. The reaction has a broad substrate scope, and various enantioenriched gem-diborylalkanes can be obtained in good yields with excellent enantioselectivity. Further elaboration of the enantioenriched gem-diborylalkanes provides access to a diverse set of valuable chiral building blocks.

Asymmetric rearrangement of racemic epoxides catalyzed by chiral Br?nsted acids

This paper describes a chiral Br?nsted acid catalyzed asymmetric 1,2-rearrangement of racemic epoxides via a hydrogen-shift process for the synthesis of chiral aldehydes, and, followed by a reduction, a variety of optically active alcohols can be furnished in moderate yields with up to 50% ee. Especially, a facile one-pot synthesis of chiral alcohols directly from simple alkenes by a sequential epoxidation, rearrangement, and reduction has also been realized.

Rhodium/tris-binaphthyl chiral monophosphite complexes: Efficient catalysts for the hydroformylation of disubstituted aryl olefins

A family of threefold symmetry phosphite ligands, P(O-BIN-OR)3 (BIN = 2,2′-binaphthyl; R = Me, Bn, CHPh2, 1-adamantyl), derived from enantiomerically pure (R)-BINOL, was developed. Cone angles within the range 240-270° were calculated for the phosphite ligands, using the computational PM6 Hamiltonian. Their rhodium complexes formed in situ showed remarkable catalytic activity in the hydroformylation of hindered phenylpropenes, under relatively mild reaction conditions, with full chemoselectivity for aldehydes, high regioselectivity, however with low enantioselectivity. The ether substituents at the ligand affected considerably the catalytic activity on the hydroformylation of 1,1- and 1,2-disubstituted aryl olefins. The kinetics of the hydroformylation of trans-1-phenyl-1-propene, using tris[(R)-2′-benzyloxy-1,1′-binaphthyl-2-yl]phosphite as model ligand, was investigated. A first order dependence in the hydroformylation initial rate with respect to substrate and catalyst concentrations was found, as well as a positive order with respect to the partial pressure of H2, and a slightly negative order with respect to phosphite concentration and CO partial pressure.

Highly enantioselective hydroformylation of aryl alkenes with diazaphospholane ligands

(Chemical Equation Presented) Asymmetric, rhodium-catalyzed hydroformylation of terminal and internal aryl alkenes with diazaphospholane ligands is reported. Under partially optimized reaction conditions, high enantioselectivity (>90% ee) and regioselectivities (up to 65:1 α:β) are obtained for most substrates. For terminal alkenes, both enantioselectivity and regioselectivity are proportional to the carbon monoxide partial pressure, but independent of hydrogen pressure. Hydroformylation of para-substituted styrene derivatives gives the highest regioselectivity for substrates bearing electron-withdrawing substituents. A Hammett analysis produces a positive linear correlation for regioselectivity.

Stereoselective Construction of Acyclic Carbon Chains by a One-Pot Coupling Process Based on Alkenyloxazoline-Titanium Complexes

A versatile organometallic intermediate, an alkenyloxazoline-titanium complex, has been developed that enables one-pot multicomponent diastereoselective and asymmetric coupling processes to be achieved in a remarkably efficient manner (see scheme).

Pseudoephedrine as a practical chiral auxiliary for the synthesis of highly enantiomerically enriched carboxylic acids, alcohols, aldehydes, and ketones

The use of pseudoephedrine as a practical chiral auxiliary for asymmetric synthesis is described in full. Both enantiomers of pseudoephedrine are inexpensive commodity chemicals and can be N-acylated in high yields to form tertiary amides. In the presence of lithium chloride, the enolates of the corresponding pseudoephedrine amides undergo highly diastereoselective alkylations with a wide range of alkyl halides to afford α-substituted products in high yields. These products can then be transformed in a single operation into highly enantiomerically enriched carboxylic acids, alcohols, aldehydes, and ketones.

Highly enantioselective hydroformylation of olefins catalyzed by rhodium(I) complexes of new chiral phosphine-phosphite ligands

A new chiral phosphine-phosphite ligand, (R)-2-(diphenylphosphino)- 1,1'-binaphthalen-2'-yl (S)-1,1'-binaphthalene-2,2'-diyl phosphite [(R,S)- BINAPHOS, (R,S)-2a], was synthesized. Its Rh(I) complex was prepared, and its structure has been characterized by 1H and 31P NMR spectroscopy. Using Rh(I) complexes of (R,S)-2a and its enantiomer, highly enantioselective hydroformylation of styrene has been performed (94% ee, iso/normal = 88/12). The catalyst system was also effective for a variety of other olefins. Some other phosphine-phosphite ligands bearing 1,1'-binaphthyl and biphenyl backbones, such as (S)-3,3'-dichloro-6-(diphenylphosphino)-2,2',4,4'- tetramethylbiphenyl-6'-yl (R)-1,1'-binaphthalene-2,2'-diyl phosphite [(S,R)- BIPHEMPHOS. (S,R)-5a], (R,R)-2a, (R,S)-2b, (R)-2c, and (R)-5b, were tested for asymmetric hydroformylation. The results indicate that the sense of enantioface selection for the prochiral olefins is mainly determined by the absolute configuration of the phosphine site, for example, the (R)-2- (diphenylphosphino)-1,1'-binaphthalen-2'-yl group in (R,S)-2a. The relative configurations of the two biaryl groups in the phosphine-phosphites play crucial roles in the degree of the enantioselectivities, that is, the (R,S)- isomer generally gives products in high ee's and the (R*,R*)-isomer does in low ee's. Treatment of Rh(acac)[(R,S)-2a] with a 1:1 mixture of carbon monoxide and hydrogen gave a hydridorhodium complex. RhH-(CO)2[(R,S)-2a], as a single species. Trigonal bipyramidal structure is suggested for this complex, in which the hydride and the phosphite moiety are located at the apical positions and the phosphine and the two carbonyls occupy the equatorial positions. The interchange of the phosphine and the phosphite sites with each other through rapid pseudorotations has not been observed in RhH(CO)2[(R,S)-2a]. The structural deviations of the monohydride complexes from an ideal trigonal bipyramid seem to be larger in (R*,R*)-isomers than in the corresponding (R*,S*)-isomers. The existence of only one active species involved in the Rh(1)-(R,S)-2a-catalyzed hydroformylation has been manifested by the plot of ln([R]/[S]) of the hydroformylation product vs the reciprocals of the reaction temperatures. The higher thermodynamic stability of Rh(acac)[(R,S)-2a] than its diastereomer Rh(acac)[(R,R)-2a] is demonstrated in relation to the restricted configuration of (R)-2c to (R,S)- 2c in its complex formation with Rh(1).