82668-85-7

Upstream product

• 74249-41-5 3-(2-bromo-1-phenylethoxy)-propene 
• 96-09-3 styrene oxide 
• 74249-40-4 2-allyloxy-2-phenylethyl tosylate 
• 102921-26-6 (1,2-dibromoethyl)benzene 
• 75455-48-0 2-allyloxy-2-phenylethan-1-ol 
• 74249-42-6 2-iodo-1-phenyl-1-((prop-2-enyl)oxy)ethane 
• 17075-00-2 2-methyl-4-phenyl-3-butyn-1-ol 
• 80735-94-0 1-Phenyl-3-buten-1-ol 
• 51558-95-3 1-phenyl-2-(phenylselanyl)ethanol 
• 100-42-5 styrene 
• 185421-42-5 phenyl 2-(allyloxy)-2-phenylethyl selenide 
• 135569-02-7 <<<(1-phenyl-3-butenyl)oxy>methyl>seleno>benzene 
• 114805-44-6 (1-Allyloxy-2,2-dichloro-ethyl)-benzene 
• 185421-63-0 phenyl(2-phenyl-2-(prop-2-yn-1-yloxy)ethyl)selane 

Downstream Products

• 41927-30-4 2-methyl-4-phenylbutan-1-ol 

Relevant academic research and scientific papers

Radical-triggered three-component coupling reaction of alkenylboronates, α-halocarbonyl compounds, and organolithium reagents: The inverse ylid mechanism

An operationally simple protocol to affect a radical addition to alkenylboronates that spontaneously undergo a [1,2]-metalate shift is described. Overall, the reaction is a three-component coupling of an organolithium, alkenylboronic ester, and halide which takes place with broad scope and good to excellent yields. Experimental mechanistic investigations support the formation of a boron inverse ylid intermediate.

Lewis Acid Mediated "endo-dig" Hydroalkoxylation-Reduction on Internal Alkynols for the Stereoselective Synthesis of Cyclic Ethers and 1,4-Oxazepanes

Lewis acid mediated 5/6/7-endo-dig hydroalkoxylation-reduction cascade on internal alkynols gave an expedient, stereoselective synthesis of cyclic ethers and 1,4-oxazepanes. The strategy has been extended to the first examples of hydroalkoxylation-alkyne

Inter- and intramolecular radical couplings of ene-ynes or halo-alkenes promoted by an InCl3/MeONa/Ph2SiH2 system

(Chemical Equation Presented) An effective generation of indium hydride (HInCl2) under nonacidic conditions is achieved by transmetalation between Ph2SiH2 and InCl2OMe. The presented system achieves the titled coupling reactions in a radical manner. In particular, the nonacidic character enables the applications to acid-sensitive inter- and intramolecular ene-yne couplings.

An efficient methodology for the C-C bond forming radical cyclization of hydrophobic substrates in water: Effect of additive on radical reaction in water

The combination of the water-soluble radical initiator, 2,2′-azobis[2-(2-imidazolin-2-yl)propane] (VA-061), water-soluble chain carrier, 1-ethylpiperidine hypophosphite (EPHP) and surfactant, cetyltrimethylammonium bromide (CTAB), was found to be the most

Indium(III) chloride-sodium borohydride system: A convenient radical reagent for an alternative to tributyltin hydride system

The indium hydride generated from NaBH4 and InCl3, is a promising candidate of alternative to Bu3SnH. In particular, the catalytic performance of InCl3 in the dehalogenation of alkyl and aryl halides, intramolecular cyclization and intermolecular coupling reaction are noteworthy. Copyright

A novel and efficient methodology for the C-C bond forming radical cyclization of hydrophobic substrates in water

Matrix presented The combination of water-soluble radical initiator 2,2′-azobis[2-(2-imidazolin-2-yl)propane] (VA-061), water-soluble chain carrier 1-ethylpiperidine hypophosphite (EPHP), and surfactant cetyltrimethylammonium bromide (CTAB) was found to b

Tetrahydrofuran derivatives from epoxides via group transfer cyclization or reductive radical cyclization of organotellurium and organoselenium intermediates

Monosubstituted epoxides were regiospecifically ring-opened from the sterically least hindered side by benzenetellurolate and benzeneselenolate reagents to afford aryl β-hydroxyalkyl tellurides and selenides, respectively. These materials were O-allylated by treatment with allylic bromides/sodium hydride in tetrahydrofuran and O-prop-2-ynylated when reacted with propargyl bromide/sodium hydride. On photolysis in benzene containing 40 mol % of hexabutylditin, the β-(allyloxy)alkyl aryl tellurides were found to undergo group transfer cyclization to afford 2-substituted 4-[(aryltelluro)methyl]tetrahydrofurans (cis/trans = 1/3-1/10). The aryl β-(prop-2-ynyloxy)alkyl tellurides similarly afforded 2-substituted 4-[(aryltelluro)methylene]tetrahydrofurans with an E/Z-ratio close to unity. The β-(allyloxy)alkyl aryl selenides and aryl β-(prop-2-ynyloxy)alkyl selenides failed to undergo group transfer cyclization. In the presence of tributyltin hydride and 2,2'-azobisisobutyronitrile, the former compounds were found to undergo reductive radical cyclization in high yields to afford 2-substituted 4-methyltetrahydrofurans (cis/trans = 1/3-1/10). Aryl β-(prop-2-ynyloxy)alkyl selenides similarly afforded 2-substituted 4-methylenetetrahydrofurans. 2-Alkoxy-2-(allyloxy)ethyl phenyl selenides, prepared by allyloxyselenenation of vinyl ethers, were found to undergo reductive radical cyclization to afford 2-alkoxy-4-methyltetrahydrofurans (cis/trans = 13-1/4). The preference for formation of trans-2,4-disubstituted tetrahydrofurans in the group transfer and reductive radical cyclizations was rationalized assuming a chairlike transition state with a preferred adoption of a pseudoequatorial position of the 2-substituent. By carrying out the reactions at lower temperatures (ambient or -45°C), using triethylborane as an initiator, it was possible to further increase the trans selectivity in the reductive cyclizations.

Scope of alkoxymethyl radical cyclizations

We have explored different aspects of the cyclization capability of alkoxymethyl radicals and report here a full account of our investigations. The required radicals were generated from (phenylseleno)-methyl ethers (e.g., 6), which were prepared from homoallylic or bis-homoallylic alcohols by a two-step process. The alcohols were alkylated with (iodomethyl)tributylstannane. The stannanes were reacted with n-BuLi, and the resulting α-alkoxyanions were trapped with diphenyldiselenide to give the (phenylseleno)methyl ethers, which were stable to chromatography. When treated with tributyltin hydride, in the presence of a radical initiator, these precursors undergo a smooth cyclization to substituted tetrahydrofurans and tetrahydropyrans. Formation of the cyclization product was found to be the primary pathway even at relatively high tin hydride concentration. The diastereoselectivity of this cyclization was comparable to that observed in other radical cyclizations. The cis selectivity in cyclization of 6 increased gradually (up to 11:1) as the reaction temperature was lowered. The cyclization can be used for the synthesis of bicyclic and tricyclic compounds and can be incorporated in systems capable of tandem cyclizations.

Cyclization of Alkoxymethyl Radicals

Alkoxymethyl radicals, generated conveniently from phenylseleno precursors, cyclize to afford substituted tetrahydrofurans and tetrahydropyrans in excellent yield and with good stereoselectivity.