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

A convenient and stereoselective synthesis of ( Z )-allyl selenides via Sm/TMSCl system-promoted coupling of Baylis-Hillman adducts with diselenides 1 first-author †E-mail:ykuiliu@zjut.edu.cnCHRC@zjut.edu.cn †E-mail:ykuiliu@zjut.edu.cnCHRC@zjut.edu.cn ykuiliu@zjut.edu.cn 1 1 corresp ‡Corresponding Author ‡Corresponding Author †E-mail:ykuiliu@zjut.edu.cnCHRC@zjut.edu.cn †E-mail:ykuiliu@zjut.edu.cnCHRC@zjut.edu.cn ykuiliu@zjut.edu.cn 2 State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, China Department of Chemistry, Zhejiang University, Hangzhou 310028, China Department of Chemistry, Zhejiang University, Hangzhou 310028, China 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 S N 2′ substitution of Baylis-Hillman adducts to produce the ( Z )-allyl selenides. Stereoselective synthesis ( Z )-allyl selenides Diselenides Baylis-Hillman adducts Sm/TMSCl system INTRODUCTION 1 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 1972 ; Fujita et al., 1998 1998 ; Carter and Bourland, 2000 2000 ), allylic homocoupling reactions (Masugama et al., 1989 1989 ), and various other chemical transformations (Shea et al., 1986 1986 ; Back and Moussa, 2002 2002 ; 2003 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 1979 ), samarium diiodide (Zhang et al., 1993 1993 ), indium (Munbunjong et al., 2005 2005 ) and lithium aluminium hydride (Suzuki et al., 1985 1985 ), etc. Other methods include reactions of organometallic reagents with organoselenium compounds (Yu et al., 1997 1997 ; Huang and Chen, 2000 2000 ), conversion from α -phenylseleno ketones (Nishiyama et al., 1982 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 1996 ; 2003 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 1996 ; 2003 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 1995 ; Chavan et al., 1997 1997 ; Yadav et al., 2001 2001 ), allyl sulfides (Calò et al., 1988 1988 ), allyl amine (Das et al., 2005a 2005a ), allyl ethers (Roy et al., 2000 2000 ), allyl phosphonates (Janecki and Bodalski, 1990 1990 ), and allyl borates (Kabalka et al., 2004 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 2005 ; 2006 2006 ) and application of samarium reagents in organic synthesis (Zhou and Zhang, 1999 1999 ; Lu and Zhang, 1999 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 1 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 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 2005b ; Basavaiah et al., 1994 1994 ; Larson et al., 1984 1984 ), in the 1 H 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. RESULTS AND DISCUSSION 1 The results are summarized in Table 1 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. 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; All products were characterized by 1 H NMR, MS and IR; Isolated yields Entry R 1 R 2 Time (h) Product b b Yield (%) c c 1 C 6 H 5 C 6 H 5 6.0 3a 90 2 C 6 H 5 4-CH 3 C 6 H 4 6.0 3b 92 3 C 6 H 5 4-CH 3 OC 6 H 4 6.0 3c 88 4 C 6 H 5 4-ClC 6 H 4 6.0 3d 91 5 C 6 H 5 3-NO 2 C 6 H 4 8.0 3e 86 6 C 6 H 5 2-furyl 6.0 3f 89 7 C 6 H 5 C 6 H 5 CH 2 CH 2 6.0 3g 92 8 C 6 H 5 n -C 7 H 15 6.0 3h 87 9 4-CH 3 C 6 H 4 C 6 H 5 6.0 3i 89 10 C 6 H 5 CH 2 4-CH 3 C 6 H 4 8.0 3j 85 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 S N 2′ substitution of selenide anions to Baylis-Hillman adducts (Fig. 2 2 ) (Ranu and Das, 2005 2005 ). CONCLUSION AND REPRESENTATIVE ANALYTICAL DATA 1 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; 1 H NMR (CDCl 3 , 400 MHz) δ : 3.79 (s, 3H, OCH 3 ), 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=); 13 C NMR (CDCl 3 , 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 C 17 H 16 O 2 Se: C 61.64, H 4.87; Found: C 61.92, H 4.77. References TG Back , Z Moussa . 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