Reactions of alkoxysulfonium salts with alkoxides

Johnson, Carl R.; Phillips, W. Gary

doi:10.1021/jo01281a049

Cited by 52 publications

(15 citation statements)

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“…Methoxydiphenylsulfonium tetrafluorborate (2) was prepared as described earlier. 4 Sodium thiophenoxide (PhSNa) was prepared by reaction of thiophenol (PhSH) with dispersed sodium in boiling diethyl ether under argon. The product (95%) was filtered and washed with dry diethyl ether.…”

Section: Methodsmentioning

confidence: 99%

“…4 Recently, we found that thianthrene cation radical perchlorate (Th Á ClO 4 À ) reacts easily with a variety of primary and secondary alcohols (Scheme 1), permitting the isolation of crystalline 5-(alkoxy)thianthrenium perchlorates (1). [5][6][7] The availability of these salts allowed us to begin a systematic study of their reactions with nucleophiles.…”

Section: -3mentioning

confidence: 99%

“…The largest systematic studies have been in reactions of hydroxide ion, alkoxide ions and alcohols with methoxy-and ethoxysulfonium ions (since those studies were used in characterizing the exchange of alkoxy ligands at the sulfur atom), the racemization of sulfoxides and the oxidation of alcohols to aldehydes and ketones. 2,4,[8][9][10][11][12] As far as we are aware, systematic or deliberate studies of reactions of alkoxysulfonium ions with halide ions have not been reported. Reactions of chloride and bromide ion with particular alkoxysulfonium ions, coincidental, for example, with, and arising from studies of, oxidations of alcohols, have been reported, [13][14][15][16] and we shall refer further to these reactions.…”

Section: -3mentioning

confidence: 99%

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Reactions of nucleophiles with 5-(alkoxy)thianthrenium ions

Liu

Shine

Zhao

1999

J. Phys. Org. Chem.

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Reactions of 5-(alkoxy)thianthrenium perchlorates (1) with weakly basic nucleophiles Br À , IÀ and PhS À (X À ) in MeCN and DMSO led to S N 2 substitution, E2C elimination, and reaction at sulfonium sulfur to extents depending on the structure of the alkoxy group (RO) in 1 and the nucleophile. Three types of reaction occurred with R = cyclopentyl (1a), cyclohexyl (1b), cis-(1c) and trans-4-methylcyclohexyl (1d) and cycloheptyl (1e), and X À = Br À and I À . That is, S N 2 reaction gave RX and thianthrene 5-oxide (ThO), E2C reaction gave cycloalkene and ThO and reaction at sulfonium sulfur gave X 2 , thianthrene (Th) and cycloalkanol (ROH). Earlier work with R = Me (1f) and Et (1g) and X À = I À , Br À had shown that only S N 2 reaction occurred. In contrast with reactions of halide ions, reactions of PhS À with 1b-g occurred only at sulfonium sulfur, giving Th, ROH and PhSSPh (DPDS). For comparison with 1, reactions of Ph 2 S OMe (2) with I À and PhS À were carried out. Reaction with I À gave only Ph 2 S=O and MeI (S N 2). Reaction with PhS À gave very little PhSMe (S N 2) but mainly Ph 2 S, MeOH, and DPDS from reaction at sulfonium sulfur. The differences in nucleophilic pathways (PhS À vs Br À and I À ) in reactions with 1 and 2 are attributed to differences in thiophilicities of the nucleophiles. The thiophilicity of PhS À dominates its reactions with 1 and 2. The direction toward products (Th, ROH and DPDS) in these reactions is compounded by the ease of displacement of alkoxide from 1 and 2 by PhS À , and the ease with which, subsequently, thiophilic PhS À attacks sulfenyl sulfur in the resulting phenylthiosulfonium ion.

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Section: Methodsmentioning

confidence: 99%

Section: -3mentioning

confidence: 99%

Section: -3mentioning

confidence: 99%

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Reactions of nucleophiles with 5-(alkoxy)thianthrenium ions

Liu

Shine

Zhao

1999

J. Phys. Org. Chem.

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“…The sulfonium cation substrates 1 are prepared by halogenation of sulfides, or by alkylation or acylation of sulfoxides. In the Pummerer reactions of alkoxysulfonium salts (3), alkylation and redox can be performed in separate steps; however, when X is halogen (4) or acyloxy (9, the intermediate sulfonium cation is not isolable, and its intervention has to be inferred by indirect means.…”

Section: Sur La Conversion De P-y-chchs(x)chmentioning

confidence: 99%

“…[3], p values range from +2.07 to +3.77 as the leaving group Y is varied from iodide to trimethylammonium (25). The increase in p for the poorer leaving group Can.…”

Section: Sur La Conversion De P-y-chchs(x)chmentioning

confidence: 99%

Stereochemical aspects of the Pummerer reaction. Regioselectivity as a criterion for the differentiation of ylide and E2 pathways in the product-determining step of the reactions of benzyl methyl halo- and oxysulfonium cations

Wolfe¹,

Kazmaier²

1979

Can. J. Chem.

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The conversion of [Formula: see text] (X = Cl, OCH3, OCOCH3, OCOCHCl2, OCOCF3) to a regioisomeric mixture of p-Y-C6H4CHXSCH3 and p-Y-C6H4CH2SCH2X has been studied as a function of X, Y, and deuteration in the benzyl and methyl positions. The conclusion is reached that, when X is acyloxy, the transformation of the sulfonium cation to an α-thiocarbonium ion and thence to the products proceeds via an E2 pathway. Trifluoroacetic anhydride is a much more reactive reagent than acetic anhydride for Pummerer reactions of benzyl methyl sulfoxides. However, with other sulfoxides, this reagent is not as effective as acetic anhydride. Acetyl trifluoroacetate is not effective as a Pummerer reagent.

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The P ummerer Reaction of Sulfinyl Compounds

Lucchi

Miotti²,

Modena³

1991

Organic Reactions

102

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The Pummerer reaction involves the formation of an α‐functionalized sulfide from a sulfoxide bearing at least one α‐hydrogen atom. The reaction can also be described as an internal redox process where the SX group is reduced and the α carbon is oxidized. The first report by Pummerer on the reaction which now bears his name appeared in 1909 and described the formation of thiophenol and glyoxylic acid on heating phenylsulfinylacetic acid with mineral acids. The products Pummerer observed resulted from hydrolysis of the initially formed α‐substituted sulfides, which are the typical products of the reaction. The term “Pummerer reaction” was later extended to the reaction of sulfoxides with acid anhydrides. Selenium and nitrogen analogs undergo similar reactions. The former is known as the seleno–Pummerer reaction, and the latter is usually referred to as the Polonovski reaction. The sila–Pummerer reaction, which is also discussed in this chapter, is the rearrangement of sulfoxides bearing a silyl group on the α carbon. From a mechanistic point of view there are many other reactions, sometimes given specific names, such as the Sommelet–Hauser, Stevens, and Vilsmeier rearrangements, that appear to resemble the Pummerer reaction. Reactions in which the sulfoxide group acts as an oxidant in an intermolecular redox process have characteristics similar to the typical Pummerer reaction. The α‐halogenation of sulfides, in which the sulfide sulfur may first be oxidized to a halosulfonium salt that rearranges to the final product, is formally similar to the Pummerer reaction. For the sake of clarity and to be as exhaustive as possible, we have limited the scope of this chapter to the restrictive definition.

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Reactions of alkoxysulfonium salts with alkoxides

Cited by 52 publications

References 1 publication

Reactions of nucleophiles with 5-(alkoxy)thianthrenium ions

Reactions of nucleophiles with 5-(alkoxy)thianthrenium ions

Stereochemical aspects of the Pummerer reaction. Regioselectivity as a criterion for the differentiation of ylide and E2 pathways in the product-determining step of the reactions of benzyl methyl halo- and oxysulfonium cations

The P ummerer Reaction of Sulfinyl Compounds

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