Skip to main content
NCBI home page
Journal of Zhejiang University. Science. B logoLink to Journal of Zhejiang University. Science. B
letter
. 2006 Apr 14;7(5):393–396. doi: 10.1631/jzus.2006.B0393

A convenient and stereoselective synthesis of (Z)-allyl selenides via Sm/TMSCl system-promoted coupling of Baylis-Hillman adducts with diselenides*

Yun-kui Liu 1,†, Dan-qian Xu 1, Zhen-yuan Xu 1,†,‡, Yong-min Zhang 2
PMCID: PMC1462932  PMID: 16615170

Abstract

A simple and convenient procedure for stereoselective synthesis of (Z)-allyl selenides has been developed by a one-pot reaction of diselenides with Baylis-Hillman adducts in the presence of samarium metal-trimethylsilyl chloride under mild conditions. Presumably, the diselenides are cleaved by Sm/TMSCl system to form selenide anions, which then undergo SN2′ substitution of Baylis-Hillman adducts to produce the (Z)-allyl selenides.

Keywords: Stereoselective synthesis, (Z)-allyl selenides, Diselenides, Baylis-Hillman adducts, Sm/TMSCl system

INTRODUCTION

Allyl selenides have drawn much attention as a class of important intermediates in organic synthesis. For example, they are useful synthetic precursors for the [1,3]- or [2,3]-sigmatropic rearrangements (Sharpless and Lauer, 1972; Fujita et al., 1998; Carter and Bourland, 2000), allylic homocoupling reactions (Masugama et al., 1989), and various other chemical transformations (Shea et al., 1986; Back and Moussa, 2002; 2003). Generally, allyl selenides are synthesized from allylic halides with selenide anions, which could be generated by reduction of diselenides with sodium borohydride (Hori and Sharpless, 1979), samarium diiodide (Zhang et al., 1993), indium (Munbunjong et al., 2005) and lithium aluminium hydride (Suzuki et al., 1985), etc. Other methods include reactions of organometallic reagents with organoselenium compounds (Yu et al., 1997; Huang and Chen, 2000), conversion from α-phenylseleno ketones (Nishiyama et al., 1982), etc. In view of their significance in organic synthesis, it is still necessary to extend the scope of allyl selenides family and develop new synthetic routes.

The Baylis-Hillman reaction is well known as one of useful carbon-carbon bond-forming reaction in the last decades (Basavaiah et al., 1996; 2003). The adducts of the reaction, 3-hydroxy-2-methylene-alkanoates (derived from acrylate esters), have been widely utilized as important precursors for stereoselective synthesis of trisubstituted alkenes (Basavaiah et al., 1996; 2003). To date, a series of heteroatom-substituted allylic derivatives transferred from Baylis-Hillman adducts have been reported, among which include allyl halides (Basavaiah et al., 1995; Chavan et al., 1997; Yadav et al., 2001), allyl sulfides (Calò et al., 1988), allyl amine (Das et al., 2005a), allyl ethers (Roy et al., 2000), allyl phosphonates (Janecki and Bodalski, 1990), and allyl borates (Kabalka et al., 2004), etc. However, to the best of our knowledge, no literature on the synthesis of Baylis-Hillman adduct-derived allyl selenides has been reported. As a continuation of our interest in Baylis-Hillman reaction (Liu et al., 2005; 2006) and application of samarium reagents in organic synthesis (Zhou and Zhang, 1999; Lu and Zhang, 1999), we report here a simple and convenient procedure for the stereoselective synthesis of (Z)-allyl selenides via one-pot reaction of diselenides with Baylis-Hillman adducts promoted by samarium-trimethylsilyl chloride system under mild conditions.

METHODS

A typical experimental procedure is as follows: under a nitrogen atmosphere, a solution of diphenyl diselenide (0.5 mmol) in THF (10 ml) was treated with samarium (1.0 mmol) and TMSCl (0.6 ml) for 2 h at room temperature until the powdered samarium was almost consumed and the yellow solution became almost colorless. Then to the mixture was added methyl 3-hydroxy-2-methylene-3-phenylpropanoate (2a) with the mixture being continuously stirred at room temperature for 4 h. After usual work-up, (Z)-methyl 2-phenylselenomethyl-3-phenylacrylate (3a) was obtained in 90% yield (Fig.1). It was shown in NOESY (nuclear overhauser effect spectroscopy) experiment that there is no NOE (nuclear overhauser effect) correlation between the signals of the internal olefin proton and the allylic methylene protons. Besides, according to literature (Das et al., 2005b; Basavaiah et al., 1994; Larson et al., 1984), in the 1H NMR spectrum of a trisubstituted alkene the β-vinylic proton, cis- and trans- to the ester group are known to resonate at δ 7.5 and δ 6.5, respectively, when alkene is substituted by an aryl group; while the same proton cis- and trans- to an ester group appears at δ 6.8 and δ 5.7, respectively, when substituted by an alkyl one. All these data suggest the products adopt Z-stereoconfiguration.

Fig. 1.

Fig. 1

Open in a new tab

Synthesis of (Z)-allyl selenides from Baylis-Hillman adducts and diselenides promoted by Sm/TMSCl system

RESULTS AND DISCUSSION

The results are summarized in Table 1. A variety of Baylis-Hillman adducts either possessing aryl groups (with donating as well as withdrawing functionalities) or alkyl ones were used in this reaction in order to establish the generality, with all reactions proceeding smoothly and giving desirable yield of products under similar conditions. As for diselenides, those dialkyl diselenides needed longer time to be cleaved by Sm/TMSCl system comprised of those diaryl diselenides. Besides good yields, the present process also exhibited excellent stereoselectivity. Only Z-stereoconfiguration of the products was obtained while no E-isomer was observed from the spectra.

Table 1.

Synthesis of (Z)-allyl selenides from Baylis-Hillman adducts and diselenides promoted by Sm/TMSCl systema

Entry R1 R2 Time (h) Productb Yield (%)c
1 C6H5 C6H5 6.0 3a 90
2 C6H5 4-CH3C6H4 6.0 3b 92
3 C6H5 4-CH3OC6H4 6.0 3c 88
4 C6H5 4-ClC6H4 6.0 3d 91
5 C6H5 3-NO2C6H4 8.0 3e 86
6 C6H5 2-furyl 6.0 3f 89
7 C6H5 C6H5CH2CH2 6.0 3g 92
8 C6H5 n-C7H15 6.0 3h 87
9 4-CH3C6H4 C6H5 6.0 3i 89
10 C6H5CH2 4-CH3C6H4 8.0 3j 85
Open in a new tab
a

Reagents and conditions: 1 (0.5 mmol), 2 (1.0 mmol), Sm (1.0 mmol), TMSCl (0.6 ml), THF (10 ml), r.t., 6.0~8.0 h;

b

All products were characterized by 1H NMR, MS and IR;

c

Isolated yields

Although the exact mechanism is not very clear to us at this moment, it is speculated that the reaction may involve a silyl enolate intermediate 2A, which is a key intermediate for facilitating the SN2′ substitution of selenide anions to Baylis-Hillman adducts (Fig.2) (Ranu and Das, 2005).

Fig. 2.

Fig. 2

Open in a new tab

Presumed mechanism for synthesis of (Z)-allyl selenides

CONCLUSION AND REPRESENTATIVE ANALYTICAL DATA

In conclusion, the Sm/TMSCl system-promoted one-pot coupling of diselenides with Baylis-Hillman adducts provides an efficient methodology for synthesizing (Z)-allyl selenides. The remarkable advantages of this process are its simple operation, mild reaction conditions, high yields and excellent stereoselectivity.

Representative analytical data for (Z)-allyl selenides. (Z)-methyl 2-phenylselenomethyl-3-phenyl-acrylate (3a): oil; 1H NMR (CDCl3, 400 MHz) δ: 3.79 (s, 3H, OCH3), 4.05 (s, 2H, methylene-H), 7.20~7.35 (m, 8H, ArH), 7.49~7.53 (m, 2H, ArH), 7.67 (s, 1H, ArCH=); 13C NMR (CDCl3, 100 MHz) δ: 25.22, 52.50, 127.78, 128.82, 128.98, 129.24, 129.63, 129.89, 130.24, 134.43, 135.11, 140.21, 168.06; IR (film) ν max: 3057, 3025, 1715, 1625, 1577, 1266 cm−1; MS m/z (%): 332 (M+). Anal. calcd. for C17H16O2Se: C 61.64, H 4.87; Found: C 61.92, H 4.77.

Footnotes

*

Project (No. 2004C21032) supported by the Key Technologies R & D Program of Zhejiang Province, China

References

  • 1.Back TG, Moussa Z. Remarkable activity of a novel cyclic seleninate ester as a glutathione peroxidase mimetic and its facile in situ generation from allyl 3-hydroxypropyl selenide. J Am Chem Soc. 2002;124(41):12104–12105. doi: 10.1021/ja028030k. [DOI] [PubMed] [Google Scholar]
  • 2.Back TG, Moussa Z. Diselenides and allyl selenides as glutathione peroxidase mimetics. Remarkable activity of cyclic seleninates produced in situ by the oxidation of allyl ω-hydroxyalkyl selenides. J Am Chem Soc. 2003;125(44):13455–13460. doi: 10.1021/ja0357588. [DOI] [PubMed] [Google Scholar]
  • 3.Basavaiah D, Sarma PKS, Bhavani AKD. Applications of the Baylis-Hillman reaction 2: a simple stereoselective synthesis of (E)- and (Z)-trisubstituted alkenes. J Chem Soc, Chem Commun. 1994;(9):1091–1092. doi: 10.1039/c39940001091. [DOI] [Google Scholar]
  • 4.Basavaiah D, Bhavani AKD, Pandiaraju S, Sarma PKS. Baylis-Hillman reaction: magnesium bromide as a stereoselective reagent for the synthesis of [E]- and [Z]-allyl bromides. Synlett. 1995;(3):243–244. doi: 10.1055/s-1995-4929. [DOI] [Google Scholar]
  • 5.Basavaiah D, Rao PD, Hyma RS. The Baylis-Hillman reaction: a novel carbon-carbon bond forming reaction. Tetrahedron. 1996;52(24):8001–8062. doi: 10.1016/0040-4020(96)00154-8. [DOI] [Google Scholar]
  • 6.Basavaiah D, Rao AJ, Satyanarayana T. Recent advances in the Baylis-Hillman reaction and applications. Chem Rev. 2003;103(3):811–891. doi: 10.1021/cr010043d. [DOI] [PubMed] [Google Scholar]
  • 7.Calò V, Lopez L, Pesce G. A simple three-step synthesis of β,β-disubstituted acrylates. J Organomet Chem. 1988;353(3):405–409. doi: 10.1016/0022-328X(88)80328-0. [DOI] [Google Scholar]
  • 8.Carter RG, Bourland TC. The first vanadium-catalyzed oxidation of aryl allylic selenides with in situ [2,3] sigmatropic rearrangement. Chem Commun. 2000;(20):2031–2032. doi: 10.1039/b006278m. [DOI] [Google Scholar]
  • 9.Chavan SP, Ethiraj KS, Kamat SK. Facile synthesis of 2E-2-chloromethyl aryl-2-enoates. Tetrahedron Lett. 1997;38(42):7415–7416. doi: 10.1016/S0040-4039(97)01744-9. [DOI] [Google Scholar]
  • 10.Das B, Mahender G, Chowdhury N, Banerjee J. Single-step stereoselective synthesis of (E)- and (Z)-allylamines from acetyl derivatives of Baylis-Hillman adducts. Synlett. 2005;(6):1000–1002. doi: 10.1055/s-2005-864822. [DOI] [Google Scholar]
  • 11.Das B, Majihi A, Banerjee J, Chowdhury N, Venkateswarlu K. A highly efficient stereoselective synthesis of (Z)- and (E)-allyl iodides from Baylis-Hillman adducts. Tetrahedron Lett. 2005;46(46):7913–7915. doi: 10.1016/j.tetlet.2005.09.097. [DOI] [Google Scholar]
  • 12.Fujita K, Kanakubo M, Ushijima H, Oishi A, Ikeda Y, Taguchi Y. A symmetric [2,3] sigmatropic rearrangement of opticallyl active allylic selenides. Synlett. 1998;(9):987–988. [Google Scholar]
  • 13.Hori T, Sharpless KB. Conversion of allylic phenylselenides to the rearranged allylic chlorides by N-chlorosuccinimide. Mechanism of selenium-catalyzed allylic chlorination of beta-pinene. J Org Chem. 1979;44(23):4208. doi: 10.1021/jo01337a047. [DOI] [Google Scholar]
  • 14.Huang Y, Chen RY. A novel synthesis of allyl selenides by reaction of an organosamarium reagent with alkyl selenocyanates. Synth Commun. 2000;30(2):377–381. [Google Scholar]
  • 15.Janecki T, Bodalski R. A convenient method for the synthesis of substituted 2-methoxycarbonyl- and 2-cyano-allylphosphonates. The allyl phosphite-allylphosphonate rearrangement. Synthesis. 1990;(9):799–801. doi: 10.1055/s-1990-27019. [DOI] [Google Scholar]
  • 16.Kabalka GW, Venkataiah B, Dong G. Pd-catalyzed cross-coupling of Baylis-Hillman acetate adducts with bis(pinacolato)diboron: an efficient route to functionalized allyl borates. J Org Chem. 2004;69(17):5807–5809. doi: 10.1021/jo0492618. [DOI] [PubMed] [Google Scholar]
  • 17.Larson GL, de Kaifer CF, Seda R, Terres LE, Ramirez JR. A stereoselective, two-step preparation of alpha-alkyl-alpha, beta-unsaturated esters. J Org Chem. 1984;49(18):3385–3386. doi: 10.1021/jo00192a028. [DOI] [Google Scholar]
  • 18.Liu YK, Li J, Zheng H, Xu DQ, Xu ZY. An atom-economical and environmentally benign preparation of unsymmetrical bis-allyl ethers via dimerization of Baylis-Hillman adducts catalyzed by cesium hydroxide monohydrate. Synlett. 2005;(19):2999–3001. [Google Scholar]
  • 19.Liu YK, Xu XS, Zheng H, Xu DQ, Xu ZY. A facile and stereoselective synthesis of unsymmetrical diallylsulfides via indium-promoted one-pot reaction of Baylis-Hillman acetates, sodium thiosulfate, and allyl bromide. Synlett. 2006;(4):571–574. [Google Scholar]
  • 20.Lu GL, Zhang YM. Facile formation of samarium(III) selenoates from potassium iodide catalyzed reaction of samarium metal and selenides, and their application in synthesis of selenoesters. Synth Commun. 1999;29(2):219–225. [Google Scholar]
  • 21.Masugama Y, Yamada K, Shimizu S. Hexacarbonylbdenum(0)-induced dechalcogenization of allylic sulfides, sulfones, and selenides: nucleophilic substitution and reductive dechalcogenization. Bull Chem Soc Jpn. 1989;62(9):2913–2918. [Google Scholar]
  • 22.Munbunjong W, Lee EH, Chavasiri W, Jang DO. Indium-mediated mild and efficient one-pot synthesis of alkyl phenyl selenides. Tetrahedron Lett. 2005;46(50):8769–8771. doi: 10.1016/j.tetlet.2005.10.025. [DOI] [Google Scholar]
  • 23.Nishiyama H, Itagaki K, Osaka N, Itoh K. Transformation of α-phenylseleno ketones to allylic selenides via migration of the phenylseleno group. Tetrahedron Lett. 1982;23(40):4103–4106. doi: 10.1016/S0040-4039(00)88359-8. [DOI] [Google Scholar]
  • 24.Ranu BC, Das A. A convenient synthesis of β-phenylselenocarbonyl compounds by in-TMSCl promoted cleavage of diphenyl diselenide and subsequent michael addition. Adv Synth Catal. 2005;347(5):712–714. doi: 10.1002/adsc.200404355. [DOI] [Google Scholar]
  • 25.Roy O, Riahi A, Henin F, Muzart J. Synergy or competition between palladium-catalysis and KF/alumina-mediation for the allylic substitution of the acetates of Baylis-Hillman adducts by phenols. Tetrahedron. 2000;56(41):8133. doi: 10.1016/S0040-4020(00)00727-4. [DOI] [Google Scholar]
  • 26.Sharpless KB, Lauer RF. Facile thermal rearrangements of allyl selenides and diselenides [1,3] and [2,3] shifts. J Org Chem. 1972;37(24):3973–3974. doi: 10.1021/jo00797a058. [DOI] [Google Scholar]
  • 27.Shea RG, Fitzner J, Fankhauser JE, Spaltenstein A, Carpino PA, Peevey RM, Pratt DV, Tenge BJ, Hopkins PB. Allylic selenides in organic synthesis: new methods for the synthesis of allyl amines. J Org Chem. 1986;51(26):5243–5252. doi: 10.1021/jo00376a037. [DOI] [Google Scholar]
  • 28.Suzuki H, Yoshinaga M, Takaoka K, Hiroi Y. A simple synthesis of aryl difluoromethyl selenides and tellurides. Synthesis. 1985;(5):497–499. doi: 10.1055/s-1985-31245. [DOI] [Google Scholar]
  • 29.Yadav JS, Reddy BVS, Madan C. Montmorillonite clay-catalyzed stereoselective syntheses of aryl-substituted (E)- and (Z)-allyl iodides and bromides. New J Chem. 2001;25(9):1114–1117. doi: 10.1039/b103850h. [DOI] [Google Scholar]
  • 30.Yu MX, Zhang YM, Bao WL. The synthesis of allyl selenides by organosamarium reagent. Synth Commun. 1997;27(4):609–613. [Google Scholar]
  • 31.Zhang YM, Yu YP, Lin RH. Cleavage of selenium-selenium and tellurium-tellurium bond by samarium diiodide: synthesis of selenoesters, telluroesters, unsymmetrical alkyl phenyl selenides and tellurides. Synth Commun. 1993;23(2):189–193. [Google Scholar]
  • 32.Zhou LH, Zhang YM. Low-valent titanium induced reductive coupling of diaryl diselenides with acid chlorides or acid anhydrides: facile synthesis of selenoesters. J Chem Res. 1999;(1):28–29. doi: 10.1039/a803235a. [DOI] [Google Scholar]

Articles from Journal of Zhejiang University. Science. B are provided here courtesy of Zhejiang University Press

RESOURCES