40888-89-9

Upstream product

• 13343-40-3 (2,2-difluoro-1-cyclopropyl)benzene 
• 93-54-9 1-Phenyl-1-propanol 
• 1459-01-4 (1-iodopropan-2-yl)benzene 
• 698-87-3 3-phenyl-2-propanol 
• 2114-39-8 (2-bromopropyl)-benzene 
• 637-50-3 1-phenylpropene 
• 1009-67-2 2-methyl-3-phenylpropanoic acid 

Downstream Products

• 103-65-1 phenylpropane 
• 1206519-41-6 C₂₁H₂₂ 
• 61380-47-0 (±)-1-phenylpropanyl-2-yl methansulfonate 

Relevant academic research and scientific papers

Open-Shell Fluorination of Alkyl Bromides: Unexpected Selectivity in a Silyl Radical-Mediated Chain Process

We disclose a novel radical strategy for the fluorination of alkyl bromides via the merger of silyl radical-mediated halogen-atom abstraction and benzophenone photosensitization. Selectivity for halogen-atom abstraction from alkyl bromides is observed in the presence of an electrophilic fluorinating reagent containing a weak N-F bond despite the predicted favorability for Si-F bond formation. To probe this surprising selectivity, preliminary mechanistic and computational studies were conducted, revealing that a radical chain mechanism is operative in which kinetic selectivity for Si-Br abstraction dominates due to a combination of polar effects and halogen-atom polarizability in the transition state. This transition-metal-free fluorination protocol tolerates a broad range of functional groups, including alcohols, ketones, and aldehydes, which demonstrates the complementary nature of this strategy to existing fluorination technologies. This system has been extended to the generation of gem-difluorinated motifs which are commonly found in medicinal agents and agrochemicals.

Nucleophilic Substitution of Aliphatic Fluorides via Pseudohalide Intermediates

A method for aliphatic fluoride functionalization with a variety of nucleophiles has been reported. Carbon–fluoride bond cleavage is thermodynamically driven by the use of silylated pseudohalides TMS-OMs or TMS-NTf2, resulting in the formation of TMS-F and a trapped aliphatic pseudohalide intermediate. The rate of fluoride/pseudohalide exchange and the stability of this intermediate are such that little rearrangement is observed for terminal fluoride positions in linear aliphatic fluorides. The ability to convert organofluoride positions into pseudohalide groups allows facile nucleophilic attack by a wide range of nucleophiles. The late introduction of the nucleophiles also allows for a wide range of functional-group tolerance in the coupling partners. Selective alkyl fluoride mesylation is observed in the presence of other alkyl halides, allowing for orthogonal synthetic strategies.

Targeted fluorination with the fluoride ion by manganese-catalyzed decarboxylation

We describe the first catalytic decarboxylative fluorination reaction based on the nucleophilic fluoride ion. The reported method allows the facile replacement of various aliphatic carboxylic acid groups with fluorine. Moreover, the potential of this method for PET imaging has been demonstrated by the successful 18F labeling of a variety of carboxylic acids with radiochemical conversions up to 50-%, representing a targeted decarboxylative 18F labeling method with no-carrier-added [18F]fluoride. Mechanistic probes suggest that the reaction proceeds through the interaction of the manganese catalyst with iodine(III) carboxylates formed in situ from iodosylbenzene and the carboxylic acid substrates. Nucleophile first: An efficient manganese porphyrin catalyzed decarboxylative fluorination reaction based on a nucleophilic fluorine source is described. The potential of the described method for use in PET imaging has been demonstrated by the successful 18F labeling of various aliphatic carboxylic acids, representing the first decarboxylative 18F labeling method with no-carrier-added [18F]fluoride.

The direct anti-Markovnikov addition of mineral acids to styrenes

The direct anti-Markovnikov addition of strong Bronsted acids to alkenes remains an unsolved problem in synthetic chemistry. Here, we report an efficient organic photoredox catalyst system for the addition of HCl, HF and also phosphoric and sulfonic acids to alkenes, with complete regioselectivity. These transformations were developed using a photoredox catalyst in conjunction with a redox-active hydrogen atom donor. The nucleophile counterion plays a critical role by ensuring high reactivity, with 2,6-lutidinium salts typically furnishing the best results. The nature of the redox-active hydrogen atom donor is also consequential, with 4-methoxythiophenol providing the best reactivity when 2,6-lutidinium salts are used. A novel acridinium sensitizer provides enhanced reactivity within several of the more challenging reaction manifolds. This Article demonstrates how nucleophilic addition reactions mediated by photoredox catalysis can change the way electrophilic and homofugal precursors are constructed.

Rearrangement and double fluorination in the deiodinative fluorination of neopentyl iodide with xenon difluoride

Alkyl iodides give products from the neopentyl rearrangement on reaction with xenon difluoride. Neopentyl iodide performs a double rearrangement and yields a gem-difluoro product, 2,2-difluoro-3-methylbutane. Studies of the mechanism show that an alkene intermediate is involved in the double rearrangement process. Alkenes can be substituted as substrates in reaction with xenon difluoride-iodine to give gem-difluoro products. 13C Labeling verifies the skeletal rearrangement process.

CATALYTIC HYDROGENOLYSIS OF 1,1-DIFLUORO-2-PHENYL-AND 1,1-DIFLUORO-3-METHYL-2-PHENYLCYCLOPROPANE.

The title compounds were hydrogenolyzed over PdO or Raney nickel. The C//2-C//3 bond of the cyclopropane ring underwent cleavage exclusively over both catalyts. The contribution of the fluorine substituent to the lengthening and weakening the C//2-C//3 bond of the cyclopropane ring seems to become a dominant factor in regioselectivity.