Isolation of the key intermediates in the catalyst-free conversion of oxiranes to thiiranes in water at ambient temperature

Kleiner, Christian M.; Horst, Luise; Würtele, Christian; Wende, Raffael C.; Schreiner, Peter R.

doi:10.1039/b820232j

Cited by 21 publications

(20 citation statements)

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“…The chemical conversion of epoxides into thiiranes in the presence of a suitable sulfur donor such as ammonium thiocyanate proceeds in water at ambient temperature and in excellent yields. 53 We envisage that a cysteine residue, activated by the A domain of the PKS-NRPS, becomes tethered to the PCP, and serves as the substrate for the cysteine desulfurase TlmS. The persulfide group forms at the TlmS active site, the other product being PCP-bound alanine, which we propose is hydrolysed by the adjacent thioesterase (TE) domain to allow the PCP to be re-charged with cysteine.…”

Section: Resultsmentioning

confidence: 99%

A genomics-led approach to deciphering the mechanism of thiotetronate antibiotic biosynthesis

et al. 2016

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Section: Resultsmentioning

confidence: 99%

A genomics-led approach to deciphering the mechanism of thiotetronate antibiotic biosynthesis

et al. 2016

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“…The concentration of organolithium reagents was determined by acid-base titration [9]. Compounds IIa [10], IIb [11], IIc [12], IId [13], IIe [14], IIf [13], IIg [15], IIh [16,17], IIi [12], IIIa [18], IIIb [19], IV [20], and V [21] were described previously; they were identified by GC-MS and 1 H and 13 C NMR data. Quantitative analysis of the reaction mixture was performed by 1 H NMR spectroscopy and GLC.…”

Section: Methodsmentioning

confidence: 99%

Reactions of 2-(α-Haloalkyl)thiiranes with nucleophilic reagents: V. Reactions of 2-(α-Chloroalkyl)thiiranes with organolithium compounds

2010

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2-(α-Haloalkyl)thiiranes reacted with methyl-, butyl-, and phenyllithium to give the corresponding allyl sulfides. The reactions of diastereoisomeric erythro-and threo-2-(1-chloroethyl)thiiranes with phenyllithium were stereospecific, and they afforded (E)-and (Z)-1-phenylsulfanylbut-2-enes, respectively. 3-Chloromethyl-2,2-dimethylthiirane and phenyllithium gave rise to a mixture of 3-methyl-3-phenylsulfanylbut-1-ene and 3-methyl-1-phenylsulfanylbut-2-ene. The reactions of 2-chloromethylthiiranes with phenyllithium and methyllithium in the presence of a catalytic amount of copper(I) iodide (10 mol %) led to the formation of substituted thiiranes as the major products. Mechanisms of the observed transformations are discussed. * For communication IV, see [1]. † Deceased.Unlike oxiranes, reactions of alkylthiiranes with organometallic compounds involve desulfurization or polymerization processes rather than opening of the three-membered ring [2][3][4]. Presumably, desulfurization occurs through intermediate formation of ate complexes and is stereospecific; furthermore, this reaction may be regarded as a method for the preparation of alkenes [2]. On the other hand, there are published data indicating that 2-(chloromethyl)thiirane (Ia) is capable of giving rise to monomeric products of formal chlorine replacement in reactions with organolithium reagents; however, these products have quite specific nature [5, 6] (Scheme 1). Unfortunately, these two examples represent all available information on such reactions which could underlie a convenient procedure for the synthesis of substituted thiiranes. Therefore, in the present work we examined reactions of the simplest organolithium compounds with some 2-(α-haloalkyl)thiiranes in diethyl ether.We found that phenyllithium and butyllithium reacted with 2-(chloromethyl)thiirane (Ia) at a fairly high rate on moderate cooling. Methyllithium was inert up to 0°C, but it did react with compound Ia in the presence of DABCO. Quite surprisingly and contrary to published data, as low-molecular products of these transformations we identified the corresponding allyl sulfides IIa-IIc (Scheme 2). 2-(Bromomethyl)thiirane (Ib) (which is less convenient to handle with) reacted with phenyllithium to give sulfide IIc in a considerably better yield.

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“…3 ) The transformation of (R)-11 to (S)-15 was described for the first time by Schreiner and coworkers [15].…”

Section: Methodsmentioning

confidence: 99%

Reaction of Optically Active Oxiranes with Thiofenchone and 1‐Methylpyrrolidine‐2‐thione: Formation of 1,3‐Oxathiolanes and Thiiranes

Fu¹,

Linden²,

Heimgartner³

2011

Helvetica Chimica Acta

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The SnCl4‐catalyzed reaction of (−)‐thiofenchone (=1,3,3‐trimethylbicyclo[2.2.1]heptane‐2‐thione; 10) with (R)‐2‐phenyloxirane ((R)‐11) in anhydrous CH2Cl2 at −60° led to two spirocyclic, stereoisomeric 4‐phenyl‐1,3‐oxathiolanes 12 and 13 via a regioselective ring enlargement, in accordance with previously reported reactions of oxiranes with thioketones (Scheme 3). The structure and configuration of the major isomer 12 were determined by X‐ray crystallography. On the other hand, the reaction of 1‐methylpyrrolidine‐2‐thione (14a) with (R)‐11 yielded stereoselectively (S)‐2‐phenylthiirane ((S)‐15) in 56% yield and 87–93% ee, together with 1‐methylpyrrolidin‐2‐one (14b). This transformation occurs via an SN2‐type attack of the S‐atom at C(2) of the aryl‐substituted oxirane and, therefore, with inversion of the configuration (Scheme 4). The analogous reaction of 14a with (R)‐2‐{[(triphenylmethyl)oxy]methyl}oxirane ((R)‐16b) led to the corresponding (R)‐configured thiirane (R)‐17b (Scheme 5); its structure and configuration were also determined by X‐ray crystallography. A mechanism via initial ring opening by attack at C(3) of the alkyl‐substituted oxirane, with retention of the configuration, and subsequent decomposition of the formed 1,3‐oxathiolane with inversion of the configuration is proposed (Scheme 5).

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Isolation of the key intermediates in the catalyst-free conversion of oxiranes to thiiranes in water at ambient temperature

Abstract: Herein we shed light on the mechanism of the reaction of epoxides with ammonium thiocyanate to give the corresponding thiiranes in water, and we present a computational mechanistic model for this highly useful reaction.

Cited by 21 publications

References 93 publications

A genomics-led approach to deciphering the mechanism of thiotetronate antibiotic biosynthesis

A genomics-led approach to deciphering the mechanism of thiotetronate antibiotic biosynthesis

Reactions of 2-(α-Haloalkyl)thiiranes with nucleophilic reagents: V. Reactions of 2-(α-Chloroalkyl)thiiranes with organolithium compounds

Reaction of Optically Active Oxiranes with Thiofenchone and 1‐Methylpyrrolidine‐2‐thione: Formation of 1,3‐Oxathiolanes and Thiiranes

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