Xanthates, allylic

Xanthates, allyl, rearrangement 702 diaryl, rearrangement 700 intermediates in formation of thiols 194-211... 

Scheme 10.17 illustrates allylation by reaction of radical intermediates with allyl stannanes. The first entry uses a carbohydrate-derived xanthate as the radical source. The addition in this case is highly stereoselective because the shape of the bicyclic ring system provides a steric bias. In Entry 2, a primary phenylthiocar-bonate ester is used as the radical source. In Entry 3, the allyl group is introduced at a rather congested carbon. The reaction is completely stereoselective, presumably because of steric features of the tricyclic system. In Entry 4, a primary selenide serves as the radical source. Entry 5 involves a tandem alkylation-allylation with triethylboron generating the ethyl radical that initiates the reaction. This reaction was done in the presence of a Lewis acid, but lanthanide salts also give good results. 

See also ALKANETHIOLS, ALKENEBIS(SULFONIUM PERCHLORATES) allyl trifluo-ROMETHANESULFONATES, ARENEDIAZO ARYL SULFIDES BIS(ARENEDIAZO) sulfides, BIS(SULFURDIIMIDES DIAZONIUM SULFATES, DIAZONIUM SULFIDES AND DERIVATIVES METAL AMIDOSULFATES, METAL PHOSPHORUS TRISULFIDES METAL SULFATES, METAL SULFIDES, NON-METAL SULFIDES SULFONIC ACID ESTERS, SULFUR BLACK, SULFUR ESTERS THIOPHENOXIDES, XANTHATES ... 

Deoxygenation of allyttc alcohols.3 A method for conversion of allylic alcohols to l-alkenes is outlined in equation (I). The first step is an allylic rearrangement of an Oallyl xanthate to 2. The second step is an allyl transfer from sulfur to tin with tri-n-butyltin hydride to give the allylic stannane (3). The last step, destannylation, is a well-known mule to terminal alkcnes.4... 

The thermal rearrangement of an allyl xanthate to a dithiocarbonate was used to introduce the sulfur atom on a quaternary carbon in the synthesis of agelasidine A, a natural S-containing sesquiterpene [494]. 

The structure of (88) is remarkable two of the xanthato ligands are bonded in a normal, terminal way whereas the other two ligands are terminally bonded to one molybdenum and tf bonded to the other other molybdenum atom as in (89)." The latter bonding type shows that a xanthate can act like an allyl ion. 

This problem is not so severe when acyl xanthates are used as precursors because these substrates absorb in the visible region, while the products do not (however, the products might still be recycled to the radical pool by radical addition-elimination). Visible light photolysis of benzoyl xanthane (42) and allyl acetate provides (43) in 60% yield. Standard (ionic) 3-elimination of the xanthane is a facile reaction that gives (44). When the tertiary acyl xanthane (45) is irradiated in the presence of W-benzylmaleimide... 

A tin-free radical cyclization of the xanthate 272 using dilauroyl peroxide (DLP), as the radical initiator, in chlorobenzene was used to give the 5//-pyrido[2,3-A azepin-8-one 273 (Scheme 35) <20040L3671>. The xanthate 272 was also made by an intermolecular free radical addition to allyl acetate, using the xanthate 271, as the radical precursor. Somewhat surprisingly in this latter case, intramolecular free radical attack on the pyridine ring did not take place. 

A number of sulfur-centered radical scavengers have been employed for Meerwein type carbothiolation reactions [109, 110]. The most prominent of those are certainly xanthates [111-113] and thiocyanates, among which the latter have received special attention recently. As shown in Scheme 21, thiocyanates are well-suited for the functionalization of activated and non-activated alkenes [114, 115]. Remarkably, the reaction of 56 with 2-methallyl chloride to give 57 is not significantly impeded by the possible (3-fragmentation of a chlorine radical, which would lead to allylation products [116]. With an activated and a non-activated alkene present in a substrate... 

The (IsQ-coordinated species [Mo(CO)3(py)3] prepared from [Mo(CO)6] and pyridine is useful for the synthesis of various jr-allyl molybdenum compounds (68JOM(13)Pl, 970M5365). The 3-allyl complexes [( 3-allyl)Mo(CO)2Br(py)2] form [( 3-allyl)Mo(CO)2(S,S)(py)] with the anionic S,S-donors, dithiocarbamates and xanthates of sodium and potassium, M (S,S) (81JOM(218)185). [( 3-C3H5)Mo(CO)2(py)2Br] (68JO M(14)375) with thallium hexafluorophosphate in acetonitrile gives... 

From the first-order rate constants obtained in different solvents (in sealed ampoules), it is apparent that this isomerization is not very sensitive to the polarity of the medium, in accordance with an isopolar, six-membered activated complex [156]. A similar small solvent effect has been observed for the [3,3]sigmatropic rearrangement of allyl S-methyl xanthate to allyl methyl dithiol carbonate [559]. 

Allylstaimanes are available from reactions of allybnagne-sium or allyllithium compounds with tin halides (equation 32). Other syntheses involve reactions of triorganotin anionic species with allylic halides or esters (equation 14), as well as reactions of allylic xanthates, tosylates, etc. with tin hydrides (equation 33). 

Organosulfone-mediated allylation, vinylation and azidation represent very effective tin-free radical processes. However, the reported methods do not work well with primary alkyl iodides and xanthate as radical precursor, owing to in-... 

The use of sulfones as relays can be extended to the introduction of a large variety of appendages. Vinylation is especially important because of the general difficulty of performing vinylations on sp centres using transition metal chemistry. The examples assembled in Scheme 14 thus acquire a special significance [31]. It is also noteworthy that both the allylation and vinylation reactions, as well as some of the more exotic transformations discussed later in this section, all of which employ sulfone-based reagents, can be applied not just to aliphatic xanthates but also to iodides and tellurides [29,37-44]. 

Unusual and otherwise difficult to obtain boronates can be made by addition of a xanthate to allyl or vinyl boronates. The reaction proceeds in the same way as for ordinary olefins and compounds containing a boronate... 

The thermal rearrangement of allylic xanthates to allylic dithiocarbonates is a well-known reaction which results in the creation of a new stereogenic carbon center when the starting xanthate contains an unsymmetrically substituted C-C double bond. Moreover, in the case of chiral xanthates this rearrangement is accompanied by the transfer of chirality from the stereogenic carbon atom in the substrate to the newly created stcrcogcnic center in the product. 

Fully stereoselective allylic xanthate to allylic dithiocarbonate rearrangement was first observed with diastereomeric 2,3-unsaturated sugar derivatives 1 and 3 which on heating (140 UC for 1 to 2 h) gave the diastereomers of 3,4-unsaturated sugar dithiocarbonates 2 and 4, respectively43. 

A crucial step in the synthesis of thiotetronic acids involves a fully stereoselective allylic xanthate to dithiocarbonate rearrangement45. Rearrangement of ethyl ( )-(4S)-2-methyl-4-[methylthio-(thiocarbonyl)thio]-2-pentenoate (7) gives ethyl (/f)-(2.S)-2-methyl-2-[methylthio(curbonyl)thio]-3-pentenoate (8) as a single diastereomer with an -configurated double bond and at least 98% ee. This value was determined by Mosher derivatization of the alcohol prepared from the dithiocarbonate in three steps. The remainder of the (5S)-thiotetronic acid synthesis is shown in the scheme. 

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