From selenoxides

In the case of the most reactive compounds, substitution at the carbon atom of diselenonium and ditelluronium dications is also a possible pathway. For example, formation of diselenide 117 from selenoxide 115 was explained by demethylation of intermediate dication 116 with trifluoroacetate anion.126 Dealkylation of salt 118, which is stable up to —20°C, leads to formation of nitrilium salt 119. The latter is transformed to amide 120 upon hydrolysis.64 Dealkylation of intermediate diselenonium dication 122 was suggested as the key step in the oxidative synthesis of 1,2,4-diselenazolidines 123 from eight-membered heterocycles 121 (Scheme 46).127... 

The regioselectivity of selenoxide elimination is similar to that observed for sulfoxides in that it takes place preferentially towards allylic, propargylic and benzylic hydrogens to form conjugated alkenes with CH3 > CH2 CH, e.g. the conjugated diene (103) was obtained from selenoxide (102 equation 40). ... 

Without additional reagents Aldehydes from selenoxides... 

Similarly, yn-elimination of PhSeOH from selenoxide 8 and selenoxides derived from selenides 9-11 in presence of H2O2 occurs below rt to produce enones in high yields. 

A 30% solution of hydrogen peroxide in water was purchased from Mallinckrodt Chemical Works. The reaction requires 2 molar equivalents of hydrogen peroxide, the first to oxidize the selenide to the selenoxide and the second to oxidize the elimination product, benzeneselenenic acid, to benzeneseleninic acid. The submitters recommend that the hydrogen peroxide solution be taken from a recently opened bottle, or titrated to verify its concentration. 

The elimination is promoted by oxidation of the addition product to the selenoxide by f-butyl hydroperoxide. The regioselectivity in this reaction is such that the hydroxy group becomes bound at the more-substituted end of the carbon-carbon double bond. The regioselectivity of the addition step follows Markovnikov s rule with PhSe+ acting as the electrophile. The elimination step specifically proceeds away from the oxygen functionality. 

The C(9)—C(16) subunit was synthesized from the same starting material. The chain was extended by a boron enolate addition to 2-methylpropenal (Step D-2). After introduction of a double bond by selenoxide elimination in Step E-4, a Claisen rearrangement was used to generate an eight-membered lactone ring (Step E-6). 

Other phosphorous compounds, as shown in Table 8, were resolved by the same procedure. The three isomeric phosphinates 27b-d containing a methyl group attached to the aryl substituent could also be resolved, irrespective of the methyl position. From the related phosphine oxides 28a d, however, only those with R=H (28a) and R=m-CH (28c) could be well resolved no satisfactory resolution could be obtained for the other isomers of 28. The efficiency of the optical resolution of alkylaryl-substituted sulfoxides and selenoxides was found to depend similarly on the type of substitution on the aryl ring. 

In another elegant approach (Scheme 18), a synthesis of 5-alkenyl-substituted 1,2,4-oxadiazoles relies upon a selenoxide. -elimination at the 5-a-carbon of the selenium resin-supported 1,2,4-oxadiazole 152. Access to compound 152 was achieved in two steps from the supported oxadiazole 150, which underwent deprotonation and alkylation at the 5-a-carbon to give the a-alkylated selenium resin 151. 1,3-Dipolar cycloaddition then gave the selenium resin-supported 1,2,4-oxadiazole 152 <2005JC0726>. 

The conversion of the polystyrene-supported selenyl bromide 289 into the corresponding acid 290 allowed dicyclohexylcarbodiimide (DCC)-mediated coupling with an amidoxime to give the 1,2,4-oxadiazolyl-substituted selenium resin 291 (Scheme 48). Reaction with lithium diisopropylamide (LDA) and allylation gave the a-sub-stituted selenium resin 292, which was then used as an alkene substrate for 1,3-dipolar cycloaddition with nitrile oxides. Cleavage of heterocycles 293 from the resin was executed in an elegant manner via selenoxide syn-elimination from the resin <2005JC0726>. 

The most versatile approach to disulfonium dications - reaction of triflic anhydride with monosulfoxides of bis-sulfides - has certain limitations in the case of selenium. Most importantly, selenoxides that contain (3-hydrogen atoms are labile.120 122 Trimethylsilyl triflate was used instead of triflic anhydride for synthesis of dication 112 from a selenoxide 111 (Scheme 43).123... 

Sulphoxides and selenoxides undergo syn elimination under thermal conditions. A 1,4-elimination of sulphenic acid from an allyl sulphoxide leads to dienes (equation 20)50. Precursor sulphoxides are generated by oxidation of corresponding sulphides. This reaction, however, did not give good results when applied to more complicated systems51. 

Glycals are also available from 2-deoxy sugars by acid- or base-induced eliminations ofanomeric substituents. These methods are limited by the availability ofthe 2-deoxy sugars, for which the glycals themselves are the most obvious synthetic precursors. However, examples of these methods (Scheme 5.43) are in the direct preparation oftri-O-benzyl-D-glucal (14) from 2-deoxy-tri-O-benzyl-D-glucopyranose (13) via its 1-O-mesylate [117], and di-O-benzyl-D-ribal (16) from the phenylselenide 15 via oxidation to the selenoxide followed by elimination [118]. 

Scheme 4.58 Chiral allenic sulfones from asymmetric selenoxide elimination.

The final products of oxidation of diarylselenides and tellurides (and sulfides as well) in the presence of nucleophiles are the corresponding chalcogen (IV) compounds. In the presence of water, the selenoxide or telluroxide (or the corresponding dihydroxy selenane or tellurane) is the final product. This still leaves several possible pathways, leveraged from early mechanistic studies done using electrochemical techniques on diaryl sulfides and outlined by Engman (Fig. 32). In these pathways, the initial radical cation can react with a nucleophile present in solution, or the dication resulting from further oxidation or disproportionation can do so. 

Allylic alcohols can also be obtained from epoxides by ring opening with a selenide anion followed by elimination via the selenoxide (see Section 6.8.3 for discussion of selenoxide elimination). The elimination occurs regiospecifically away from the hydroxy group.116 117 118... 

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