1275593-50-4

Upstream product

• 618-89-3 methyl 3-bromobenzoate 
• 672-65-1 (1-chloroethyl)benzene 
• 329976-80-9 potassium (1-phenylethyl)trifluoroborate 
• 14900-39-1 phenylvinylboronic acid 
• 29415-97-2 methyl 3-bromo-4-hydroxybenzoate 
• 1275593-52-6 (S)-methyl 3-(1-phenylethyl)-4-(trifluoromethyl sulfonyloxy)benzoate 
• 1275593-43-5 (S)-methyl 4-hydroxy-3-(1-phenylethyl)benzoate 
• 389068-26-2 methyl 4-hydroxy-3-(1-phenylvinyl)benzoate 

Relevant academic research and scientific papers

Enantioselective Reductive Cross-Coupling of Aryl/Alkenyl Bromides with Benzylic Chlorides via Photoredox/Biimidazoline Nickel Dual Catalysis

The asymmetric reductive arylation and alkenylation of benzylic chloride under photoredox/nickel dual catalysis using chiral biimidazoline (BiIm) ligand is reported to access 1,1-diaryl alkanes and aryl allylic compounds with good yield as well as stereo-

Nickel-catalyzed cross-coupling of photoredox-generated radicals: Uncovering a general manifold for stereoconvergence in nickel-catalyzed cross-couplings

The cross-coupling of sp3-hybridized organoboron reagents via photoredox/nickel dual catalysis represents a new paradigm of reactivity for engaging alkylmetallic reagents in transition-metal-catalyzed processes. Reported here is an investigation into the mechanistic details of this important transformation using density functional theory. Calculations bring to light a new reaction pathway involving an alkylnickel(I) complex generated by addition of an alkyl radical to Ni(0) that is likely to operate simultaneously with the previously proposed mechanism. Analysis of the enantioselective variant of the transformation reveals an unexpected manifold for stereoinduction involving dynamic kinetic resolution (DKR) of a Ni(III) intermediate wherein the stereodetermining step is reductive elimination. Furthermore, calculations suggest that the DKR-based stereoinduction manifold may be responsible for stereoselectivity observed in numerous other stereoconvergent Ni-catalyzed cross-couplings and reductive couplings.

Single-electron transmetalation in organoboron cross-coupling by photoredox/nickel dual catalysis

The routine application of Csp3-hybridized nucleophiles in cross-coupling reactions remains an unsolved challenge in organic chemistry. The sluggish transmetalation rates observed for the preferred organoboron reagents in such transformations are a consequence of the two-electron mechanism underlying the standard catalytic approach. We describe a mechanistically distinct single-electron transfer-based strategy for the activation of organoboron reagents toward transmetalation that exhibits complementary reactivity patterns. Application of an iridium photoredox catalyst in tandem with a nickel catalyst effects the cross-coupling of potassium alkoxyalkyl- and benzyltrifluoroborates with an array of aryl bromides under exceptionally mild conditions (visible light, ambient temperature, no strong base). The transformation has been extended to the asymmetric and stereoconvergent cross-coupling of a secondary benzyltrifluoroborate.

Highly enantioselective hydrogenation of styrenes directed by 2′-hydroxyl groups

A new synthetic strategy that turns styrene-type olefins into excellent substrates for Rh-catalyzed asymmetric hydrogenation by installing a 2′-hydroxyl substituent is described. This methodology accommodates trisubstituted olefinic substrates in various E/Z mixtures, leading to valuable benzylic chiral compounds including (R)-tolterodine. It is also demonstrated that the 2′-hydroxyl groups could be readily removed in high yield without loss of ee from the products. Thus, this technology represents an attractive alternative to the Ir(P-N) catalyst system for the asymmetric hydrogenation of unfunctionalized olefins.