Convenient syntheses of α-mercaptomethyl phosphonates

Makomo, Hubert; Masson, Serge; Saquet, Monique

doi:10.1016/s0040-4039(00)79302-6

Cited by 17 publications

(3 citation statements)

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“…a Spectral data of 3a are in accordance with the reported values. 3 b Satisfactory microanalyses were obtained: S ±0.6%.…”

Section: Methodsmentioning

confidence: 94%

“…Among the a-heterosubstituted phosphonates, phosphonoproline I and 2-phosphonotetrahydrofuran II have attracted interest due to their potential biological activity and synthetic applications in olefination reactions. 1,2 Previously, the sulfur analog 2-phosphonothiolane III (Figure 1) has been prepared by two methods: a low yield Michaelis-Arbuzov reaction between 2-chlorothiolane and a trialkyl phosphite 2 (without description of the obtained product) and, more recently by a four-step synthesis developed in our laboratory in racemic and asymmetric version, 3,4 starting from a dialkyl or di-(l)-menthyl phosphite. To study the reactivity of 2-phosphonothiolanes and their sulfoxides as new Horner-Wadsworth-Emmons (H-W-E) reagents, more efficient and direct ways are needed for their synthesis.…”

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confidence: 99%

“…(s, C-8,8'), 21.2 (s, C-9), 21.3 (s, C-9'), 22.0 (s, C-10), 22.1 (s, C-10'), 22.9 (s, C-5,5'), 25.4 (s, C-7), 25.5 (s, C-7'), 31.4 (d, J = 9.87, PCHCH 2 ), 31.6 (s, C-3,3'), 32.4 (d,3 J C,P = 3.59, SCH 2 CH 2 ); 33.2 (d, J = 3.59, SCH 2 ), 34.2 (s, C-4,4'), 42.4 (d, J = 156.18, PCH), 43.2 (s, C-2), 43.9 (s, C-2'), 48.8, 48.9 (2 d, J = 6.28, J = 7.18, C-6,6'), 77.7 (d, J = 7, C-1), 78.2 (d, J = 8.07, C-1') (7) Various solvents (CH 2 Cl 2 , Et 2 O, THF, CHCl 3 ) and reagents (TFAA or TMSOTf, Ac 2 O, ClSiMe 3 ) were used from r.t. to -78°C. (8) The modest yield obtained with (MeO) 3 P is due to the sensitivity of the corresponding phosphonate ester in acidic medium (partial demethylation leading to phosphonic acid derivatives).…”

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One-Step Synthesis of 2-Phosphonothiolanes by a New Pummerer-Phosphorylation Reaction: Stereoselective S-Oxidation

Marchand¹,

Gulea²,

Masson³

et al. 2001

Synthesis

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A new one-pot Pummerer phosphorylation reaction allowed an efficient synthesis of 2-phosphonothiolanes starting from thiolane S-oxide and trialkyl phosphites. The S-oxidation of these cyclic sulfides occurred with a total trans-stereoselectivity.Among the a-heterosubstituted phosphonates, phosphonoproline I and 2-phosphonotetrahydrofuran II have attracted interest due to their potential biological activity and synthetic applications in olefination reactions. 1,2 Previously, the sulfur analog 2-phosphonothiolane III ( Figure 1) has been prepared by two methods: a low yield Michaelis-Arbuzov reaction between 2-chlorothiolane and a trialkyl phosphite 2 (without description of the obtained product) and, more recently by a four-step synthesis developed in our laboratory in racemic and asymmetric version, 3,4 starting from a dialkyl or di-(l)-menthyl phosphite. To study the reactivity of 2-phosphonothiolanes and their sulfoxides as new Horner-Wadsworth-Emmons (H-W-E) reagents, more efficient and direct ways are needed for their synthesis. Herein, we describe a facile and general one-pot preparation of racemic 2-phosphonothiolanes via a new Pummerer type reaction and demonstrate the total trans-stereoselectivity of their oxidation into sulfoxides. Figure 1 Structures of a-heterosubstituted phosphonates I-IIIThe Pummerer reaction has been extensively studied and used in synthesis. Some of its applications involve the addition of a nucleophile (such as alcohol, thiol, amine or sulfide) to the intermediate sulfonium or thionium ion. 5 To our knowledge, no example involving a nucleophilic phosphorus derivative has been described. However, a recent paper has reported the possibility to trap a thionium ion (generated by addition of HCl to a vinyl sulfide) by a trialkyl phosphite with the eventual formation of an a-alkylthiophosphonate. 6 This result led us to attempt the preparation of 2-phosphonothiolanes by addition of trialkyl phosphite to a Pummerer intermediate, generated from thiolane S-oxide.We found that the treatment of thiolane S-oxide 1 with one equivalent of trifluoroacetic anhydride in diethyl ether, followed by addition of 2.2 equivalents of triisopropyl phosphite led to the 2-diisopropylphosphonothiolane 3a (Scheme 1). This was easily performed on a 10 g scale with 91% yield after purification. Scheme 1Following this first positive result, we investigated the scope of this reaction starting from other sulfoxides (pentamethylene-, dimethyl-, and phenyl methyl sulfoxide), 7 but we could not find conditions to generate the phophorylated derivatives in significant yield (formation of the trifluoroacetoxy derivative mainly occurred). Therefore, this Pummerer-phosphorylation reaction seems characteristic of the more rigid five-membered ring thiolane S-oxide 1. 2-Trifluoroacetoxythiolane (2) was not detected in the crude mixture, even when the phosphite addition was delayed. This suggests that the thionium ion B, is not Downloaded by: York University libraries. Copyrighted material.

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“…a Spectral data of 3a are in accordance with the reported values. 3 b Satisfactory microanalyses were obtained: S ±0.6%.…”

Section: Methodsmentioning

confidence: 94%

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confidence: 99%

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confidence: 99%

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