60066-58-2

Upstream product

• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 115-80-0 Triethyl orthopropionate 
• 104-54-1 3-Phenylpropenol 
• 219925-46-9 ethyl orthopropionate 
• 108-95-2 phenol 
• 60066-61-7 ethyl 3-phenyl-4-pentenoate 
• 74-88-4 methyl iodide 
• 21040-45-9 Cinnamyl acetate 
• 56161-86-5 C₅H₉BrO₂Zn 

Downstream Products

• 72524-19-7 ethyl 2,2-dimethyl-3-phenyl-4-pentenoate 

Relevant academic research and scientific papers

Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes

A mild, metal-free, atmospheric oxygen-mediated radical hydrothiolation of alkenes (and alkyne) is reported. A variety of sulfur containing motifs including alkanethiols, thiophenols and thioacids undergo an atmospheric oxygen-mediated radical hydrothiolation reaction with a plethora of alkenes in good yield with excellent functional group compatibility, typically with short reaction times to furnish a range of functionalized products. Biomolecules proved tolerant to the conditions and the procedure is robust and easily executable requiring no specialized equipment. Concise mechanistic studies confirm the process proceeds through radical intermediates in a thiol-ene reaction manifold. The methodology offers an efficient “green” approach for thiol-ene mediated “click” ligation and a milder alternative to thermally initiated hydrothiolation processes.

A Sequential Acyl Thiol-Ene and Thiolactonization Approach for the Synthesis of δ-Thiolactones

A novel strategy for the synthesis of δ-thiolactones from inexpensive and readily available ?-unsaturated esters has been developed. This strategy incorporates a radical acyl thiol-ene reaction as the key C-S bond forming step. Cyclization is achieved via a Steglich-type thiolactonization of 5-mercaptopentanoic acids. We report the facile and scalable synthesis of δ-thiolactones in moderate to good yield under mild reaction conditions with tolerance for a range of functional groups.

Acyclic Stereoselection in the Ortho Ester Claisen Rearrangement

The ortho ester Claisen rearrangement of trisubstituted allylic alcohols exhibits significant levels of diastereoselection. In E allylic alcohols, a 1,3-diaxial interaction develops in the chairlike transition state leading to the anti isomer, rendering the reaction syn selective by a factor of 3-5 to 1. In Z allylic alcohols, the 1,3-diaxial interaction develops in the transition state leading to the syn isomer, generating an anti:syn selectivity of 6-15 to 1. The relative stereochemistry of the syn isomer was confirmed independently by the synthesis of the mycotoxin botryodiplodin.

Stereoselective Acid-Catalyzed Claisen Rearrangements

An alkyl substituent in the 2-position of an E trisubstituted allylic alcohol confers significant diastereoselectivity on ortho ester and ketal Claisen rearrangements of the system.

PALLADIUM CATALYZED ALLYLATION OF REFORMATSKY REAGENTS. SYNTHESIS OF γ,δ-UNSATURATED ESTERS.

Reformatsky reagents regioselectively react under mild conditions with allylic acetates in the presence of Pd(PPh3)4 to give γ,δ-unsaturated esters in good yields.

Process for preparing dihalovinylcyclopropanecarboxylates

Novel syntheses of dihalovinylcyclopropanecarboxylates, including potent insecticides, are described. The processes begin with the reaction between an alkenol and an orthoester to produce a γ-unsaturated carboxylate, followed by the catalyzed addition of a carbon tetrahalide to the double bond and dehydrohalogenation to produce a cyclopropane derivative.

Competitive - and -Sigmatropic Rearrangements

Several cases of the oxy-Cope rearrangement, which typically prefers the -sigmatropic route, are now known to occur in a -sigmatropic fashion.By contrast, the symmetry-allowed thermal rearrangement of carbanions (or their enol derivatives; e.g.,