79929-85-4

Upstream product

• 75-11-6 diiodomethane 
• 36004-04-3 ethyl (E)-1-phenylbut-1-en-3-ol 
• 593-71-5 Chloroiodomethane 
• 104974-60-9 rac-(Z)-4-phenylbut-3-en-2-ol 
• 14371-10-9 (E)-3-phenylpropenal 
• 676-58-4 methylmagnesium chloride 
• 74-95-3 1,1-dibromomethane 
• 1896-62-4 (E)-benzalacetone 
• 74087-85-7 3,3-dimethyldioxirane 
• 1588-56-3 trans-2-phenyl-1-ethylcyclopropane 
• 917-64-6 methyl magnesium iodide 
• 34271-31-3 trans-2-phenylcyclopropanecarbaldehyde 

Downstream Products

• 79929-86-5 cis-1-(1-acetoxyethyl)-2-phenylcyclopropane 
• 79929-88-7 trans-5-phenyl-2-heptene 
• 1745-16-0 5-phenylpent-2-ene 

Relevant academic research and scientific papers

Tandem cyclopropanation with dibromomethane under Grignard conditions

(Chemical Equation Presented) Tertiary Grignard reagents and dibromomethane efficiently cyclopropanate allylic (and certain homoallylic) magnesium and lithium alcoholates at ambient temperature in ether solvents. Lithium (homo)allyl alcoholates are directly cyclopropanated with magnesium and CH 2Br2 under Barbier conditions at higher temperatures. The reaction rates depend on the substitution pattern of the (homo)allylic alcoholates and on the counterion with lithium giving best results. Good to excellent syn-selectivities are obtained from α-substituted substrates, which are in accord with a staggered Houk model. In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl carboxylates or vinyloxiranes. Using this methodology, numerous fragrance ingredients and their precursors were efficiently converted to the corresponding cyclopropyl carbinols.

Preparation of aryl-substituted E-homoallylic bromides from cyclopropylcarbinol and PBr3

An expeditious synthesis of aryl substituted E-homoallylic bromides has been accomplished by the cleavage of cyclopropylcarbinols with phosphorus tribromide. Copyright Taylor & Francis Group, LLC.

The thionophosphate-thiolophosphate photoisomerization proceeds predominantly through a non-chain radical pathway. Synthetically viable benzylation of tetrahydrofuran, propan-2-ol and olefins

The photoirradiation of thionophosphates, ROP(S)(OEt)2, derived from benzyl and vinylogously benzyl alcohols in CH3CN, with a Hanovia medium-pressure mercury lamp in a quartz vessel leads to the formation of the corresponding thiolophosphates, RSP(O)(OEt)2, through a non-chain radical pathway. This behavior of thionophosphates is unlike that of the related phosphates, which react through ionic dissociation-recombination processes. When the irradiation is conducted in solvents such as PriOH, THF and toluene, benzylation of these solvents takes place in synthetically respectable yields. Irradiation of thionophosphates in CH3CN leads to a convenient allylic benzylation of olefins.

Dimethyldioxirane hydroxylation of a hypersensitive radical probe: Supporting evidence for an oxene insertion pathway

Dimethyldioxirane oxidation of the hypersensitive radical probe (trans- 2-phenylcyclopropyl)ethane gave non-rearranged hydroxylation products consistent with an oxene insertion mechanism for the reaction.

Magnesium promoted cyclopropanation reactions of allylic alcohols

Treatment of allylic alcohols 1 with various magnesium reagents in the presence of alkyl dihalides affords the corresponding cyclopropyl alcohols 2. Reactions occur under mild conditions, and excellent diastereoselectivities have been achieved.

Samarium-Promoted Cyclopropanation of Allylic Alcohols

The use of samarium/mercury amalgam in conjunction with diiodomethane or chloroiodomethane to generate samarium carbenoids for the efficient cyclopropanation of allylic alcohols is discussed.These hydroxyl-directed cyclopropanations occur under mild conditions and allow a wide range of substitution about both the olefin and the carbinol carbon in allylic alcohol substrates.High yields and high diastereoselectivities are observed for many substrates.

Reaction of Organoaluminium Reagents with Cyclopropylmethyl Acetates and 2-Vinylcyclopropane-1,1-dicarboxylate Esters

Ring-opening alkylation of cyclopropylmethyl acetates was studied.The acetoxyl group of 7-(1-acetoxyheptyl)norcarane is substituted by the alkyl group upon treatment with trialkylaluminium, but alkylation of trans-1-(1-acetoxyethyl)-2-phenylcyclopropane with trialkylaluminium gives rise to trans-5-phenyl-2-alkenes.The reaction of (1S,2S)-2-phenylcyclopropylmethyl acetate with trimethylaluminium resulted in the complete loss of optical activity to give racemic 4-phenyl-1-pentene.Alkylation of trans-1-(1-acetoxy-3-phenylpropyl)-2-vinylcyclopropane with trialkylaluminium proceeds under regioselective ring-opening to give 3-alkylated trans-8-phenyl-1,5-octadiene (selectivity 73-83percent).The regio- and stereochemistry of homoconjugate addition to activated vinylcyclopropanes having a doubly carbonyl substituted ring carbon was studied.Trialkylaluminium on addition to diethyl 2-vinylcyclopropane-1,1-dicarboxylate in a 1,5-manner afford diethyl (2-alkyl-3-butenyl)propanedioate (over 96percent selectivity).In contrast, the reaction of this cyclopropane with tetraalkylaluminiumlithium takes place in a 1.7-manner to give diethyl (trans-4-alkyl-2-butenyl)propanedioate with 88-92percent selectivity.Clean regiocontrol of the reaction is observed in the methylation of ethyl exo-6-(trans-1-propenyl)-2-oxobicyclo(3.1.0>hexane-1-carboxylate with trimethylaluminium or tetramethyl aluminiumlithium.Alkylation with trimethylaluminium proceeds with 86percent inversion of the configuration at C(6) of the substrate, affording (2R*,3R*)-2-ethoxycarbonyl-3-cyclopentanone which is transformed into neonepetalactone.