123078-69-3

Upstream product

• 4747-36-8 (1‐cyclobutylvinyl)benzene 
• 123078-58-0 2-cyclobutyl-2-phenylpropiophenone 

Relevant academic research and scientific papers

Synthesis of (R)-2-diphenylphosphino-2′-diphenylphosphinomethyl-1,1′-binaphthyl and its use for asymmetric hydrogenation of α-alkylstyrenes

A new chiral bisphosphine ligand ((R)-2-diphenylphosphino-2′-diphenylphosphinomethyl-1,1′-binaphthyl) was synthesized from enantiomerically pure (R)-1,1′-binaphthalene-2,2′-diol. Rhodium(I) complexes of this bisphosphine ligand have been used as catalysts for asymmetric hydrogenation of α-alkylstyrenes to give the corresponding aromatic hydrocarbons in up to 77% ee.

Reductive activation and hydrofunctionalization of olefins by multiphoton tandem photoredox catalysis

The conversion of olefin feedstocks to architecturally complex alkanes represents an important strategy in the expedient generation of valuable molecules for the chemical and life sciences. Synthetic approaches are reliant on the electrophilic activation of unactivated olefins, necessitating functionalization with nucleophiles. However, the reductive functionalization of unactivated and less activated olefins with electrophiles remains an ongoing challenge in synthetic chemistry. Here, we report the nucleophilic activation of inert styrenes through a photoinduced direct single electron reduction to the corresponding nucleophilic radical anion. Central to this approach is the multiphoton tandem photoredox cycle of the iridium photocatalyst [Ir(ppy)2(dtbbpy)] PF6, which triggers in situ formation of a high-energy photoreductant that selectively reduces styrene olefinic π bonds to radical anions without stoichiometric reductants or dissolving metals. This mild strategy enables the chemoselective reduction and hydrofunctionalization of styrenes to furnish valuable alkane and tertiary alcohol derivatives. Mechanistic studies support the formation of a styrene olefinic radical anion intermediate and a Birch-type reduction involving two sequential single electron transfers. Overall, this complementary mode of olefin activation achieves the hydrofunctionalization of less activated alkenes with electrophiles, adding value to abundant olefins as valuable building blocks in modern synthetic protocols.

Ring and C-O Bond Fragmentation as Tools for Fingerprinting the Extent of Homolysis during Base-Catalyzed Carbon-Carbon Bond Cleavages of the Haller-Bauer, Cram, and Gilday Types

The mechanisms of the base-catalyzed cleavage of non-enolizable ketones (Haller-Bauer reaction), fragmentation of the alkali-metal salts of diphenylcarbinols (Cram cleavage), and decarboxylative elimination of methyllithium-carboxylic acid adducts (Gilday process) are probed by attaching a small ring or a carbon-oxygen bond proximal to the ultimate seat of reaction.Particular attention is given to whether product formation in the first case is accompanied by fission of the cyclopropane or cyclobutane subunit.The product distributions constitute a serviceable diagnostic of the relative extent to which carbanion and radical pathways operate concurrently.This distinction is also possible in the oxa analogues since the homolysis/heterolysis dichtomy is matched by retention of an intact C-O bond and the extent of its cleavage, respectively.A key feature of the Haller-Bauer process is its ability to deliver debenzoylated products having intact cyclopropane or cyclobutane rings because of its strong predilection for the generation of carbanions during C-C bond fragmentation.Counterion influences are minimal.The Cram cleavages show a very different product distribution profile.The results can be plausibly fitted to the involvement of free radicals, although the distinction between direct C-C bond hemolysis or heterolysis followed by rapid black-electron transfer cannot be made at this time.Because the Gilday reaction leads directly to styrenes and these products suffer destruction under the reaction conditions, this transformation lacks synthetic value in this particular context.