1499-63-4

Upstream product

• 766-04-1 benzyllithium 
• 21490-63-1 2,3-trans-epoxybutane 
• 6921-34-2 benzylmagnesium chloride 
• 917-64-6 methyl magnesium iodide 
• 5445-77-2 2-benzylpropionaldehyde 
• 1589-82-8 phenylmagnesium bromide 
• 56102-14-8 2-methyl-3-(phenylsulfanyl)propanal 
• 544-97-8 dimethyl zinc(II) 
• 108-88-3 toluene 
• 25181-26-4 (1α,2β,3β)-1,2-dimethyl-3-phenylcyclopropane 
• 7653-96-5 r-1-phenyl-cis-2,cis-3-dimethylcyclopropane 
• 925669-95-0 2,3-cis-epoxybutane 
• 882030-73-1 r-1,c-2-dimethyl-c/t-3-phenylcyclopropane 
• 151-50-8 potassium cyanide 

Downstream Products

• 125830-08-2 (2R*,3R*)-2-methoxy-3-methyl-4-phenylbutane 
• 125830-10-6 (2S*,3R*)-2,3-dimethyl-4-phenylbutanecarbonitrile 
• 3968-91-0 (Z)-1-phenyl-2-methyl-2-butene 
• 125830-08-2 (2S*,3R*)-2-methoxy-3-methyl-4-phenylbutane 
• 125830-10-6 (2R*,3R*)-2,3-dimethyl-4-phenylbutanecarbonitrile 

Relevant academic research and scientific papers

Diastereoselective Copper-Mediated Cross-Couplings between Stereodefined Secondary Alkylcoppers with Bromoalkynes

A copper(I)-mediated cross-coupling of stereodefined secondary alkyllithiums with bromoalkynes provided stereodefined alkynes with high diastereoselectivity (dr up to 98:2). This cross-coupling was extended to various secondary alkyllithiums bearing a remote oxygen functionality, and the alkyne synthesis was also performed with optically enriched alkyl iodides (up to 99% ee) providing, after cross-coupling, alkynes bearing two stereocenters (dr = 93:7; up to 99% ee).

N-heterocyclic carbene-catalyzed hydrosilylation of styryl and propargylic alcohols with dihydrosilanes

Reducing alkenes to tears: Addition of structurally diverse N-heterocyclic carbenes (NHCs) to silicon allows the reduction of propargylic and styryl alcohols through an organocatalyzed silylation/direct hydride transfer tandem reaction (see scheme). Catalytic turnover is enabled by the switch to and from hypervalent silicon. This provides a new synthetic application of NHC-main group element complexes. Copyright

Diastereoselective addition of organozinc reagents to 2-alkyl-3- (arylsulfanyl)propanals

The preparation of compounds incorporating the 3-hydroxy-2-methyl-1-alkyl moiety of high diastereomeric purity is described. Such compounds can serve as potential building blocks for the preparation of several kinds of natural products. Diastereoselective synthesis of two potential pine sawfly pheromone components, one the pure racemic threo-isomer of 3-methylpentadecan-2-ol and the other the racemic erythro-isomer of 3-methyltridecan-2-ol are described. The diastereoselective addition of R2Zn (R=Me, Et and n-Bu) to several 2-alkyl-3-(arylsulfanyl)propanals in the presence of a Lewis acid and CH 2Cl2 as solvent was studied. An excellent diastereomeric ratio (95/5 anti-Cram/Cram) was obtained with 2-[(phenylsulfanyl)methyl] pentanal, 2-[(phenylsulfanyl)methyl]decanal and 2-[(phenylsulfanyl)methyl] dodecanal and Me2Zn in the presence of TiCl4. (a) Lewis acid catalysed dimethylzinc addition; (b) 1. Prot. and oxidation to sulfone, 2. Alkylation; (c) Deprot. and desulfonation; (d) Desulfurisation.

Three-electron S(N)2 reactions of arylcyclopropane cation radicals. 1. Mechanism

The mechanism of photosensitized nucleophilic substitution reactions on arylcyclopropanes was investigated. Stereochemical experiments with methanol, water, and cyanide as nucleophiles showed that the reactions occurred stereospecifically with complete inversion of configuration at the carbon atom undergoing substitution. Independent generation of the arylcyclopropane cation radicals by nanosecond transient methods showed that they reacted rapidly with nucleophiles with kinetics that were first-order in both the cation radical and the nucleophiles. Through a combination of transient kinetics and steady-state Stern-Volmer quenching experiments, the reaction of the phenylcyclopropane cation radical with methanol was kinetically correlated with the formation of the substitution product. The reaction of phenylcyclopropane cation radical with a series of alcohols as nucleophiles showed small steric effects.

Amphiphilic Reactions by Means of Exceptionally Bulky Organoaluminum Reagents. Rational Approach for Obtaining Unusual Equatorial, Anti-Cram, and 1,4 Selectivity in Carbonyl Alkylation

Exceptionally bulky, oxygenophilic organoaluminum reagents, methylaluminum bis(2,6-di-tert-4-alkylphenoxide) (MAD and MAT), have been successfully utilized for stereoselective activation of carbonyl moiety.Combination of MAD or MAT with carbon nucleophiles such as organolithiums or Grignard reagents generates a new amphiphilic reaction system in which the alkylation may be interpreted as the nucleophilic addition of a reactive organometallic compound to an electrophilically activated carbonyl substrate in order to account for the regio- and stereochemical consequences.In contrast to the ordinary alkylations, the amphilic alkylation disclosed herein would be categorized into the new, yet unexplored class of alkylation that exhibits high chemoselectivity to carbonyl compounds, and more significantly it allows excellent equatorial and anti-Cram selectivity in carbonyl alkylations, hitherto difficult by the existing methodologies.Further, unusual conjugate addition of organolithium reagents to α,β-unsaturated carbonyl compounds has been accomplished by using the amphiphilic reaction system.