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Hydrides radical reactions, homolytic hydrogen atom

It is important to emphasize that the hydroxy dithioketal cyclization can be conducted under mild reaction conditions and can be successfully applied to a variety of substrates.15 However, the utility of this method for the synthesis of didehydrooxocane-contain-ing natural products requires the diastereoselective, reductive removal of the ethylthio group. Gratifyingly, treatment of 13 with triphenyltin hydride and a catalytic amount of the radical initiator, azobisisobutyronitrile (AIBN), accomplishes a homolytic cleavage of the C-S bond and furnishes didehydrooxocane 14 in diastereo-merically pure form (95 % yield), after hydrogen atom transfer. [Pg.736]

With this information in hand, it seemed reasonable to attempt to use force field methods to model the transition states of more complex, chiral systems. To that end, transition state.s for the delivery of hydrogen atom from stannanes 69 71 derived from cholic acid to the 2.2,.3-trimethy 1-3-pentyl radical 72 (which was chosen as the prototypical prochiral alkyl radical) were modeled in a similar manner to that published for intramolecular free-radical addition reactions (Beckwith-Schicsscr model) and that for intramolecular homolytic substitution at selenium [32]. The array of reacting centers in each transition state 73 75 was fixed at the geometry of the transition state determined by ah initio (MP2/DZP) molecular orbital calculations for the attack of methyl radical at trimethyltin hydride (viz. rsn-n = 1 Si A rc-H = i -69 A 6 sn-H-C = 180°) [33]. The remainder of each structure 73-75 was optimized using molecular mechanics (MM2) in the usual way. In all, three transition state conformations were considered for each mode of attack (re or ) in structures 73-75 (Scheme 14). In general, the force field method described overestimates experimentally determined enantioseleclivities (Scheme 15), and the development of a flexible model is now being considered [33]. [Pg.351]

A direct hydrogen atom transfer has been shown to occur, on the other hand, from neutral 19-electron transients obtained by one-electron reduction of saturated cationic hydrides. These derivatives apparently have a reduced acidity relative to cationic 17-electron complexes, while the presence of an unpaired electron in an orbital which may have an M-H a component may further contribute to weaken the M-H bond homolytically. An example is provided by complex CpCoH(dppe), which forms as a transient by one-electron reduction of [CpCoH(dppe)]". Cobaltocene is a strong radical scavenger, and has sufficient reducing power to carry our the reduction of the cationic cobalt hydride. Thus, reaction of the Co(III) hydride complex with two equivalents of cobaltocene affords CpCoCCjHg) in 80 % isolated yields, according to the proposed mechanism of Scheme 19 [25]. [Pg.179]

Leardini and Spagnolo have investigated the generation of iminyl radicals from azides via hydrogen atom transfer in the presence of tin hydride. Depending on the nature of the iminyl radicals, homolytic aromatic substitution was observed as well as conversion to the corresponding nitrile (Scheme 8.50, top). j8-Fragmentation of carbamoyl radicals has been observed as major reaction pathway with a-azidoamides (Scheme 8.50, bottom). [Pg.263]

Stannyl radicals are usually generated by homolytic substitution at hydrogen in a tin hydride, or at tin in a distannane, or, conjugatively, at the y-carbon atom in an allylstannane.453 The initiator is commonly AIBN at ca. 80 °C. In the presence of a trace of air, organoboranes are oxidized by a radical chain mechanism, and triethylborane is now commonly used as an initiator at temperatures down to —78°C,519 and it can be used in aqueous solution.520 9-Borabicyclo[3.3.1]nonane (9-BBN) has similarly been used to initiate the reaction of tin hydrides at 0 and —78°C,521 and diethylzinc works in the same way.522... [Pg.864]

A radical initiator, such as azobisisobutyronitrile (AIBN, 7) decomposes homolytically under reaction conditions to generate 8 which abstracts a hydrogen from tributyltin hydride (9) creating a tin-centered radical 10. The tin radical attacks at the sulphur atom of the thiocarbonyl derivative 2, generating intermediate 11 which collapses leaving tributyltin xanthate 12 (which can further decompose to 0=C=S and 13) and alkyl radical 14. Intermediate 14 can abstract another atom of hydrogen from tributyltin hydride to generate the desired alkane product 3, and replenish the pool of tin radical 10. [Pg.615]


See other pages where Hydrides radical reactions, homolytic hydrogen atom is mentioned: [Pg.13]    [Pg.13]    [Pg.44]    [Pg.174]    [Pg.390]    [Pg.192]    [Pg.145]    [Pg.208]    [Pg.208]    [Pg.181]    [Pg.114]    [Pg.34]    [Pg.208]    [Pg.484]    [Pg.139]    [Pg.309]    [Pg.74]    [Pg.443]    [Pg.721]    [Pg.183]    [Pg.252]    [Pg.199]    [Pg.97]    [Pg.46]    [Pg.240]    [Pg.10]   


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Atom/radical reactions

Homolytic

Homolytic reactions

Homolytic reactions hydrogen atoms

Hydride hydrogenation

Hydriding reaction

Hydrogen atom, reactions

Hydrogen hydrides

Radicals homolytic

Reactions hydrides

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