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Cyclization radicals

Radical addition to alkenes has been used in cyclizations in aqueous media. Oshima and co-worker studied triethylborane-induced atom-transfer radical cyclization of iodoacetals and iodoacetates in water. Radical cycMzation of the iodoacetal proceeded smoothly both in aqueous methanol and in water. Atom-transfer radical cycMzation of allyl iodoacetate is much more efficient in water than in benzene or hexane. For instance, treatment of allyl iodoacetate with triethylborane in benzene or hexane at room temperature did not yield the desired lactone. In contrast, the compound cyclized much more smoothly in water and yielded the corresponding y-lactone in high yield (Eq. 3.31). [Pg.49]


Effects of substituent on the regiochemistry of the 5-hexenyl radical cyclization... [Pg.146]

Table 12.3. Regioselectivity of Radical Cyclization as a Function of Ring Size "... Table 12.3. Regioselectivity of Radical Cyclization as a Function of Ring Size "...
The use of radical cyclizations to make five-membered rings has become a very important tool for synthetic chemists Although there has been a virtual explosion of reports in the literature regarding the cyclization of 5-hexenyl radicals to cyclopentyl carbinyl radicals in all types of hydrocarbon systems [55], the use of this cyclization for the synthesis of fluorme-containing cyclopentanes has been largely ignored... [Pg.815]

Bromobenzy 1)-1,4-dihydro-3-methoxycarbonyIpyridine (135a) upon treatment with BusSnH undergoes intramolecular radical cyclization to give both... [Pg.296]

The synthetic utility of radical cyclization was used as the key step in a four-step synthesis of the natural product (d,0-epilupinine (134b, a quinolizidine alkaloid) (75CB1043) from methyl nicotinate (146). Thus, l-(4-bromobutyl)-3-methoxycarbonyl-l,4,5,6-tetrahydropyridine (140), obtained from methyl nicotinate (146), was cyclized to 141 (43%), which on reduction with LiAlH4 in THF provided 134b in 95% yield (89T5269). [Pg.298]

Free-radical cyclization in the synthesis of N-heterocycles 97T17543. [Pg.221]

Regio- and stereocontrolled radical cyclizations in syntheses of alkaloids 97YZ973. [Pg.227]

Total syntheses of racemic Melinonine E (316) and Strychnoxanthine (317) were performed using a radical cyclization process as the key step (98JOC968). Melinonine E was first isolated from the bark of Strychnos melinoniana in 1957 (57HCA1167), but structure elucidation was not carried... [Pg.146]

Radical cyclization of perhydro-l,3-benzoxazines 64, promoted by Bu4SuH in the presence of AIBN gave a mixture of perhydropyrido[2,l-6][1,3]benzoxazin-9-ones 65 and 66 and seven membered tricyclic derivatives 67 and 68, formed in a 6-exo and 7-endo cyclization process, respectively (99TL2421). Cyclization of parent acrylamide 64 (R = R = H) occured with moderate regioselectivity (6-exo/7-endo ratio 65 35) and poor stereoselectivity (65/66 ratio 42 43). The presence of a /3-methyl group in... [Pg.186]

Scheme 1. Radical cyclization strategy for the synthesis of sativene (8) and copacamphene (9) by Bakuzis and coworkers. Scheme 1. Radical cyclization strategy for the synthesis of sativene (8) and copacamphene (9) by Bakuzis and coworkers.
In an effort to identify a more stereoselective route to dihydroagarofuran (15), trimethylsilylated alkyne 17 was utilized as a substrate for radical cyclization (Scheme 2). Treatment of 17 with a catalytic amount of AIBN and tri-n-butyltin hydride (1.25 equiv) furnishes a mixture of stereoisomeric vinyl silanes 18 (72% combined yield) along with an uncyclized reduction product (13% yield). The production of stereoisomeric vinyl silanes in this cyclization is inconsequential because both are converted to the same alkene 19 upon protodesiiyiation. Finally, a diastereoselective di-imide reduction of the double bond in 19 furnishes dihydroagaro-... [Pg.384]

Scheme 3. Selected vinyl radical cyclizations developed by Stork and coworkers. Scheme 3. Selected vinyl radical cyclizations developed by Stork and coworkers.
Vinyl radicals can also participate in 6-exo cyclizations. In pioneering work, Stork and his group at Columbia University showed that stereoisomeric vinyl bromides 20 and 21 (see Scheme 3) can be converted to cyclohexene 22.7 The significance of this finding is twofold first, the stereochemistry of the vinyl bromide is inconsequential since both stereoisomers converge upon the same product and second, the radical cyclization process tolerates electrophilic methoxycarbonyl groups. The observation that the stereochemistry of the vinyl bromide is inconsequential is not surprising because the barrier for inversion of most vinyl radicals is very low.8 This important feature of vinyl radical cyclization chemistry is also exemplified in the conversion of vinyl bromide 23 to tricycle 24, the key step in Stork s synthesis of norseychellanone (25) (see Scheme 4).9 As in... [Pg.385]

Scheme 4. Stork s vinyl radical cyclization strategy for the synthesis of norseychellanone (25)... Scheme 4. Stork s vinyl radical cyclization strategy for the synthesis of norseychellanone (25)...

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4- pentenyl radical cyclization

5-Hexenyl radical cyclization alkyl substituted

5-Hexenyl radical cyclizations

5-exo radical cyclizations

5-hexenyl radical, diastereoselective cyclization

6- exo radical cyclization

6-Heptenyl radical cyclization stereoselectivity

6-exo-trig radical cyclization

6’Endo radical cyclization

9-endo-trig radical cyclization

A-Acylamino radical cyclization

A-Amino radicals reductive cyclization

Acetal-Tethered Radical Cyclizations

Acyclic radical cyclization

Acyclic radical cyclization stereoselectivities

Acyl Radical Cyclization Approaches

Acyl radical cyclization

Acyl radicals cyclizations

Acylamino radicals cyclizations

Acyloxy radicals cyclization

Acylsilane, radical cyclization

Aldehydes radical cyclizations

Alkene radical cyclization

Alkenes radical cyclizations

Alkenyl radicals cyclization

Alkoxy radicals cyclization

Alkyl azides radical cyclizations

Alkyl nitronates radical cyclization

Alkyl radical addition-cyclization

Alkyl radical cyclization

Alkyl radicals carbocycle formation via cyclization

Alkyl radicals, dichlororadical cyclizations

Alkynes free radical cyclization

Alkynes radical cyclizations

Allenes radical cyclization

Allyl alcohols radical cyclization

Allyl carbonates radical cyclization

Allyl radical cyclization

Amidyl radicals cyclizations

Amino radicals cyclizations

Amino radicals) intramolecular cyclization

Aminyl radicals cyclizations

Aminyl-radical cyclization

And radical cyclization

Arenediazonium salts radical cyclizations

Aryl Radical Cyclizations with Grignard Reagent

Aryl azides radical cyclizations

Aryl halides radical cyclizations

Aryl radical cyclizations

Aryl radical, intramolecular cyclization

Asymmetric epoxidation radical cyclizations

Asymmetric radical cyclization reaction

Atom transfer radical cyclization

Atom transfer radical cyclization ATRC)

Atom transfer radical cyclization copper complexes

Atom transfer radical cyclization reactions

Azahexenyl radicals cyclizations

Azole system, radical cyclization

Baldwin rules, radical cyclization

Barton method radical cyclizations

Barton reaction radical cyclizations

Boron oxidative/radical cyclizations

Boron-tethered radical cyclizations

Bridged rings via radical cyclizations

Bu3SnH radical cyclization

Butenyl radicals cyclizations

CYCLIZATION, free radical 2+2] Cycloaddition reactions, with

Carbohydrates synthesis via radical cyclization

Carbonyl compounds intramolecular radical cyclization

Carbonyl radical cyclization

Carbonyloxy radicals cyclizations

Cascade radical cyclization

Cascade radical cyclization of biradicals

Catalysis of Radical Cyclizations

Catalysis radical cyclization

Catalytic radical cyclization

Copper catalyzed reactions transfer radical cyclization

Copper hydride radical cyclizations

Coriolin via tandem radical cyclization

Cyclic nitronates radical cyclization

Cyclic radical cyclization

Cyclic radical cyclization stereoselectivities

Cyclizable radical probe

Cyclization 3- butenyl radicals

Cyclization 6-heptenyl radical

Cyclization Reactions of Silyl Radicals

Cyclization alkoxyl radical

Cyclization aryl radical

Cyclization by radical reactions

Cyclization cyclobutyl radicals

Cyclization donor radical cations

Cyclization of 6-heptenoyl radicals

Cyclization of 7-octenoyl radicals

Cyclization of Alkoxyl Radicals

Cyclization of alkyl radicals

Cyclization of free radicals

Cyclization of silyl radical

Cyclization of the 5-hexenyl radical

Cyclization of unsaturated radicals

Cyclization of vinyl radicals

Cyclization peroxy! radical

Cyclization radical addition

Cyclization radical anion

Cyclization radical cations

Cyclization radical clock

Cyclization radical homolytic additions

Cyclization radical-mediated

Cyclization reactions donor radical cations

Cyclization reactions electrophilic or radical attack

Cyclization reactions free-radical

Cyclization reactions radical anions

Cyclization reactions radical cations

Cyclization substituted radicals

Cyclization vinyl radical

Cyclization, 5-hexenyl radical intermediate

Cyclization, of alkenyl radicals

Cyclization, of radicals

Cyclization, radical phenylthio-alkenes

Cyclization, radicals 2 + 2 + 2]-cycloaddition

Cyclization, radicals Diels-Alder

Cyclization, radicals Diels-Alder reaction

Cyclization, radicals alkenes with aldehydes

Cyclization, radicals alkynes

Cyclization, radicals allenes with alkenes

Cyclization, radicals calculations

Cyclization, radicals carbenes

Cyclization, radicals compounds

Cyclization, radicals compounds cycloaddition

Cyclization, radicals diradical mechanism

Cyclization, radicals electronic effects

Cyclization, radicals enantioselectivity

Cyclization, radicals ketones

Cyclization, radicals mechanism

Cyclization, radicals metal catalyzed

Cyclization, radicals orbital overlap

Cyclization, radicals photochemical

Cyclization, radicals stereochemistry

Cyclization, radicals steric effects

Cyclization, radicals thermal

Cyclization, radicals transition states

Cyclization, radicals with alkenes

Cyclization, radicals with alkynes

Cyclization, radicals with allenes

Cyclization, radicals with benzynes

Cyclization, radicals with cyclopropanes

Cyclization, radicals with dienes

Cyclization, radicals with enamines

Cyclization, radicals with imines

Cyclization, radicals with ketenes

Cyclization, radicals with nitrile oxides

Cyclization, radicals with strained compounds

Cyclizations Using Aryl Radicals

Cyclizations of Acyl Radicals

Cyclizations of Ketyl Radicals

Cyclizations of nitrogen radicals in pyrrolidine

Cyclizations of nitrogen radicals in pyrrolidine synthesis

Cyclized radicals, intermolecular

Cyclized radicals, steric factors

Cyclohexane derivatives free radical cyclizations

Cyclopentane, synthesis via radical cyclization

Deoxygenative radical cyclization

Dialdehydes radical cyclization

Diels-Alder reactions radical cyclizations

Dienes radical cyclization

Electrolytic radical cyclization

Enynes free-radical cyclization

Esker, J. L., Newcomb, M., The Generation of Nitrogen Radicals and their Cyclizations

Ester-Tethered Radical Cyclizations

Ethers, halomethylsilyl radical cyclization

Fragmentation reactions radical cyclization

Free radical cyclization kinetic control

Free radical cyclization stereochemistry

Free radical cyclization synthesis

Free radical cyclizations

Free radicals cyclization

Free radicals unsaturated, cyclization

Free-radical additions and cyclizations

Fused rings radical cyclizations

Generation of nitrogen radicals and their cyclizations

Generation of nitrogen radicals and their cyclizations for

Halo-alkenes, radical cyclization

Haloacetals, radical cyclizations

Halogen atom transfer addition reactions radical cyclizations

Halogen atom transfer reactions radical cyclizations

Heptenyl radicals cyclizations

Heteroatom radical cyclizations

Hydrogen atom transfer reactions radical cyclizations

Hydrostannylation radical cyclization

Hypnophilin via tandem radical cyclization

Iminoyl Radical Cyclizations

In radical cyclization

Indolines radical cyclization

Intramolecular Cyclizations Involving Anion Radicals

Intramolecular Free Radical Cyclizations

Intramolecular radical cyclizations

Intramolecular radical-induced cyclization

Intramolecular radical-induced stereoselective cyclization

Intramolecular reactions free radical cyclizations

Intramolecular reactions free-radical cyclization

Iodine atom transfer reactions radical cyclizations

Iron-catalyzed reactions radical cyclization

Ketones radical cyclizations

Ketyl radical cyclization

Ketyls radical cyclizations

Kolbe reactions radical cyclizations

Lactams intramolecular radical cyclization

Lactones radical cyclization

Lithium naphthalene radical cyclization

Manganese acetate radical cyclizations

Metal salts, addition radical cyclization

Michael addition radical cyclization

Michael-type radical cyclization

Morphans via radical cyclization

Nitrogen radicals, generation and cyclization

Nitrogen-centered radicals cyclizations

Nitronates radical cyclization

Octenyl radicals cyclization

Of nitrogen radicals and their cyclizations

Of nitrogen radicals and their cyclizations nucleus

Of pyrrolidines by nitrogen radical cyclization

Organocobalt complexes radical cyclizations

Organocobalt radical cyclizations

Organozinc reagents radical cyclizations

Oxidation radical cyclizations

Oxidative free-radical cyclization

Oxidative radical cyclization

Oxidosqualene radical cyclization

Oxime ethers radical cyclization

Oximes-alkenes, radical cyclization

Oxy radicals cyclizations

Oxygen-centered radicals cyclizations

Pentadienyl radical, cyclization

Pentenyl radicals cyclizations

Peroxide-mediated radical cyclization

Peroxyl radicals, cyclization

Phenylative Radical Cyclization with Phenyl Grignard Reagent

Phenylthio, radical cyclization

Polyenes radical cyclization

Pschorr reaction radical cyclizations

Pyrrolidines, generation by radical cyclizations

Quinoline RADICAL CYCLIZATION

Radical Anion-Mediated Cyclizations

Radical Bergman cyclization

Radical Cyclization of -lodo Allylic Acetals with EtMgBr

Radical Cyclizations in Alkaloid Synthesis

Radical Fragmentations, Rearrangements and Cyclizations

Radical Myers—Saito cyclization

Radical cation cyclizations

Radical cyclization Fukuyama indole synthesis

Radical cyclization azepine synthesis

Radical cyclization carbocyclics

Radical cyclization carbon-centered radicals

Radical cyclization concentration effects

Radical cyclization forming five-membered

Radical cyclization forming furan rings

Radical cyclization forming pyrans

Radical cyclization heteroatom systems

Radical cyclization heterocycles

Radical cyclization intramolecular

Radical cyclization of tertiary alcohol

Radical cyclization reductive lithiation

Radical cyclization ring size preference

Radical cyclization stereoselective

Radical cyclization stereoselectivity

Radical cyclization tetrahydropyridines

Radical cyclization tin mediated

Radical cyclization with R3 SnH

Radical cyclization, also

Radical cyclization, with

Radical cyclization, with amides

Radical cyclization, with amidyl radicals

Radical cyclization, with enamides

Radical cyclization, with ethers

Radical cyclization, with lactams

Radical cyclization, with polyenes

Radical cyclization, with pyroglutamate

Radical cyclization, with pyrroles

Radical cyclization, with trimethylsilyl derivatives

Radical cyclization, with vinyl radicals

Radical cyclizations

Radical cyclizations acyl radicals

Radical cyclizations annulation reactions

Radical cyclizations carbocyclization

Radical cyclizations carbon-centered radicals

Radical cyclizations chain methods

Radical cyclizations complexes

Radical cyclizations fragmentation method

Radical cyclizations intermolecular

Radical cyclizations nonchain methods

Radical cyclizations reductive, chromium

Radical cyclizations stereoselectivity

Radical cyclizations via alkene addition

Radical formation and cyclization

Radical olefin cyclization

Radical oxidative cyclization with

Radical oxidative cyclization with ammonium nitrate

Radical reaction cyclization

Radical reactions/cyclizations

Radical-and Nucleophilic Cyclization

Radical-based cyclizations

Radical-chain cyclizations

Radical-chain cyclizations thiol-catalyzed

Radical-mediated cyclizations

Radicals cyclizations to aromatic rings

Radicals hexenyl, cyclization

Radicals nitrogen, cyclization

Radicals radical-mediated cyclizations

Radicals unsaturated, cyclization

Regioselectivity radical cyclization

STORK Radical cyclization

Samarium diiodide radical cyclizations

Samarium iodide radical cyclizations

Samarium lactone radical cyclization

Selenoesters radical cyclization

Selenyl radical, cyclization

Self-terminating radical reactions cyclizations

Seychellene via radical cyclization

Silicon-tethered radical cyclization

Silyl radical cyclization

Silyl-tethered radical cyclization

Silyl-tethered radical cyclizations

Silylmethyl radicals cyclization

Silylmethyl radicals cyclizations

Single-electron transfer radical cyclization

Spiro compounds via radical cyclizations

Stannyl radical addition-cyclization

Stereoisomers vinyl radical cyclization

Stereoselectivity, free radical cyclizations

Stork s vinyl radical cyclization

Subject Radical-71-cyclization transform

Sulfonamides radical cyclization reactions

Sulfones, allyl radical cyclizations

Synthesis of pyrrolidines by nitrogen radical cyclization

Tandem Radical Cyclizations and Alkylations

Tandem radical addition/cyclization

Tandem radical addition/cyclization reactions

Tandem radical cyclization

Tandem radical cyclizations

Temporary Tethering Strategies in Radical Cyclization Reactions

Tertiary radical cyclization

Tether-directed Radical Cyclization Approaches to the Synthesis of C-Glycosides

Tether-directed radical cyclization

Tethered radical cyclization

The a-(bromomethyl)dimethylsilyl ether in radical cyclizations

Triquinanes radical cyclization transforms

Triquinanes radical cyclizations

Ueno-Stork radical cyclization

Unsaturated acetals, radical-chain cyclizations

Use of Unsaturated Systems Cyclization as a Free Radical Proof

Vinyl epoxides radical cyclization

Vinyl radicals cyclizations

Vitamin radical cyclization

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