Sodium tetrachloroaurate(III) dihydrate-catalyzed efficient synthesis of 1,5-benzodiazepine and quinoxaline derivatives

Sodium tetrachloroaurate(III) dihydrate-catalyzed efficient synthesis of 1,5-benzodiazepine and quinoxaline derivatives first-author †E-mail:ykuiliu@zjut.edu.cngreensyn@zjut.edu.cn †E-mail:ykuiliu@zjut.edu.cngreensyn@zjut.edu.cn ykuiliu@zjut.edu.cn corresp ‡Corresponding Author ‡Corresponding Author †E-mail:ykuiliu@zjut.edu.cngreensyn@zjut.edu.cn †E-mail:ykuiliu@zjut.edu.cngreensyn@zjut.edu.cn ykuiliu@zjut.edu.cn 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 Both 1,5-benzodiazepine and quinoxaline derivatives are important heterocycles in pharmaceuticals. We describe an efficient and clean method for the synthesis of 1,5-benzodiazepines from o -phenylenediamine and ketones catalyzed by sodium tetrachloroaurate(III) dihydrate under mild conditions. The catalyst was shown to be equally effective for the synthesis of quinoxalines from o -phenylenediamine and α-bromo ketones under the similar reaction conditions. This method produced good yields. 1,5-benzodiaepines o -phenylenediamine Ketones Quinoxalines Gold catalyst Introduction 1 Benzodiazepines and quinoxalines have recently received much attention as important classes of heterocyclic compounds in pharmaceuticals. The benzodiazepine derivatives have been found to have wide applications in medical chemistry, such as anti-convulsant, anti-anxiety, analgesic, hypnotic, sedative, antidepressant and anti-inflammatory agents (Smalley, 1979 1979 ; Landquist, 1984 1984 ; Randall and Kappel, 1973 1973 ). In addition, 1,5-benzodiazepines are intermediates used for the synthesis of other fused ring compounds such as triazolo-, oxazino- or furano-benzodiazepines (Essaber et al., 1998 1998 ; El-snyed et al., 1999 1999 ; Xu et al., 1999 1999 ; Zhang et al., 1999 1999 ; Reddy et al., 2000 2000 ). On the other hand, quinoxaline derivatives have also shown a broad spectrum of biological activities, which has led them to be privileged structures in drug discovery (Zaragoza and Stephensen, 1999 1999 ; Wu and Ede, 2001 2001 ). To date, several methods for the preparation of 1,5-benzodiazepines have been reported in the literatures, including condensation reactions of o -phenylenediamine with α,β-unsaturated carbonyl compounds (Ried and Stahlofen, 1957 1957 ), β-haloketones (Ried and Torinus, 1959 1959 ) or ketones promoted by BF 3 ·Et 2 O (Herbert and Suschitzky, 1974 1974 ), NaBH 4 (Morales et al., 1986 1986 ), polyphosphoric acid or SiO 2 , (Jung et al., 1999 1999 ), MgO/POCl 3 (Balakrishna and Kaboudin, 2001 2001 ), Yb(OTf) 3 (Curini et al., 2001 2001 ), Al 2 O 3 /P 2 O 5 or AcOH under microwave (Kaboudin and Navaee, 2001 2001 ), ionic liquid (Jarikote et al., 2003 2003 ), SmI 2 (Luo et al., 2005 2005 ), HBF 4 -SiO 2 (Bandgar et al., 2006 2006 ), dodecyl sulfonic acid (Sharma et al., 2007 2007 ), AgNO 3 (Kumar et al., 2006 2006 ), H 14 [NaP 5 W 30 O 110 ] (Heravi et al., 2007a 2007a ), polyaniline-sulfate salt (Srinivas et al., 2007 2007 ), and 2,4,6-trichloro-1,3,5-triazine (Kuo et al., 2008 2008 ). Meanwhile, a number of methods have also been developed for the synthesis of quinoxalines, involving condensation of 1,2-diamines with 1,2-dicarbonyl compounds (Kaupp and Naimi-Jamal, 2002 2002 ; More et al., 2005 2005 ; 2006 2006 ; Bhosale et al., 2005 2005 ; Heravi et al., 2007b 2007b ), 1,4-addition of 1,2-diamines with 1,2-diaza-1,3-butadienes (Aparicio et al., 2006 2006 ), oxidation-trapping of α-hydroxy ketones with 1,2-diamine (Raw et al., 2004 2004 ; Kim et al., 2005 2005 ; Robinson and Taylor, 2005 2005 ), cyclization-oxidation of polymer-linked 2-nitrophenyl carbamate with α-bromo ketones (Singh et al., 2003 2003 ), and oxidative-coupling of epoxides with o -phenylenediamine (Antoniotti and Duñach, 2002 2002 ). However, many of these procedures for the syntheses of 1,5-benzodiazepines and quinoxalines have limitations, i.e., harsh reaction conditions, high catalyst loading, occurrence of several side products, tedious work-up procedures, use of toxic and/or hazardous transition metals, and so on. Therefore, the development of clean and efficient methods for the syntheses of these valuable compounds is desirable. Gold is a soft transition metal showing high electrophilic affinity to alkynes, alkenes, and allenes (Hashmi and Hutchings, 2006 2006 ; Gorin and Toste, 2007 2007 ; Hashmi, 2007 2007 ; Hashmi and Rudolph, 2008 2008 ; Li et al., 2008 2008 ). It can also act as a Lewis acid for the activation of electrophiles (Arcadi et al., 2006 2006 ). Recently, there has been growing interest in gold-catalyzed organic transformations because gold catalysts usually exhibit extraordinary reactivity and show high selectivity in the reactions. Besides, gold catalysts are quite robust, and most of the reactions tolerate both oxygen and acidic protons; thus, neither air nor humidity needs to be excluded. As part of our ongoing interest in the gold-catalyzed transformations (Liu et al., 2009a 2009a ; 2009b 2009b ), we herein described clean and efficient syntheses of 1,5-benzodiazepines and quinoxaline derivatives using sodium tetrachloroaurate(III) dihydrate as catalyst under mild reaction conditions. Materials and methods 1 A representative procedure for the synthesis of 1,5-benzodiazepines 3 or quinoxalines 5 is described as follows: to a 25-ml flask, o -phenylenediamine 1 (0.11 g, 1.0 mmol), NaAuCl 4 ·2H 2 O (0.008 g, 0.02 mmol), ketones 2 (2.2 mmol, for synthesis of 3 ) or α-bromo ketones 4 (1.2 mmol, for synthesis of 5 ), and EtOH (5 ml) were added. The mixture was stirred at room temperature for the given time in Table 2 2 (for 3 ) or Table 3 3 (for 5 ). Upon completion, the solvent was removed under vacuum. The residue was purified by chromatography using cyclohexane/ethyl acetate (6:1, v/v) as eluent to afford 1,5-benzodiazepines 3 or quinoxalines 5 . http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546552&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546552&type=small http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546552&type=middle http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546552&type=small http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546557&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546563&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546557&type=middle http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546568&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546568&type=small http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546568&type=middle http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546568&type=small http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546574&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546578&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546574&type=middle Results and discussion 1 Initially, the reaction of o -phenylenediamine 1 with acetone 2e was tested as a model reaction for optimization of the reaction conditions (Table 1 1 ). In the absence of a gold catalyst, the reaction could hardly take place (Entry 1). The reaction proceeded smoothly to give the desired product 3e in 80% yield when 1 and 2e were treated with 2% (mole fraction) of AuCl 3 at room temperature for 5 h (Entry 2). Under the catalysis of HAuCl 4 ·4H 2 O, the yield of 3e was increased to be 85% (Entry 3). So far, the best result was obtained by using NaAuCl 4 ·2H 2 O as a catalyst, which gave 3e in 95% yield (Entry 4). Solvent screening experiments showed that ethanol is the best choice for the reaction (Entries 4–8). It is noteworthy that the reaction could still proceed well even in water or solvent-free condition (Entries 9 and 10). http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546585&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546585&type=small http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546585&type=middle http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546585&type=small http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546590&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546595&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=23546590&type=middle With optimized conditions in hand, a variety of substrates were used in this reaction to establish the generality and efficiency (Fig. 1 1 , Table 2 2 ). In most cases, the reaction proceeded smoothly to give 3 in good to excellent yields under mild conditions. Reactions of o -phenylenediamine with acetophenones possessing electron-withdrawing groups generally gave better yield of 3 than those containing electron-donating groups (Entries 4 vs. 2, 3). Both acyclic and cyclic alkylketones were suitable substrates for the reaction (Entries 5–10). Note that lower yields were obtained from the more hindered alkylketones (Entries 5–7 vs. 8). The condensation of 2-butanone 2f or 4-methyl 2-pentanone 2g with o -phenylenediamine selectively gave 3f or 3g , respectively (Entries 6 and 7), along with small amount of the diastereoisomer 3f′ or 3g′ . Encouraged by the successful application of NaAuCl 4 ·2H 2 O as a catalyst in the synthesis of 1,5-benzodiazepines, we expected that quinoxalines 5 will be obtained if o -phenylenediamine 1 is allowed to react with α-bromo ketones 4 (Das et al., 2007 2007 ). Indeed, when 1 equivalent of 1 was treated with 1.2 equivalents of 4 in ethanol under similar reaction conditions, quinoxalines 5 were produced in high yields (Fig. 2 2 , Table 3 3 ). Control experiment showed that much lower yield of 5a (33%) was obtained in the absence of the gold catalyst (Entry 1). A variety of aromatic ring-tethered α-bromo ketones were investigated to establish the scope and generality of the reaction, and in all cases quinoxalines 5 were produced in good to excellent yields in the presence of NaAuCl 4 ·2H 2 O under mild reaction conditions. In the reaction, gold catalyst may act as a bifunctional catalyst; namely, it serves as a Lewis acid catalyst to help the cyclization process via activation of the carbonyl group (Yang et al., 2007 2007 ) as well as an oxidative catalyst for the dehydrogenation of the in situ generated dihydroquinoxalines with dioxygen (Zhu and Angelici, 2007 2007 ; Liu et al., 2009a 2009a ). Conclusion 1 In summary, we described a clean and efficient protocol for syntheses of 1,5-benzodiazepines and quinoxalines. The advantages of the present method lie in relatively low catalyst loading, mild reaction conditions, simple operation, and good yields. Experimental details 1 All the starting chemicals were commercial products (Aldrich or J & K Chemica). Melting points were measured on a Büchi B-545 and uncorrected. Infrared (IR) spectra were recorded on a Bruker EQUINOX 55 spectrometer. 1 H NMR and 13 C NMR spectra were obtained on a Bruker AVANCE III 500 (500 MHz) instrument in CDCl 3 using tetramethylsilane (TMS) as internal standard. Chemical shifts ( δ ) are expressed in ×10 −6 and coupling constants ( J ) are given in Hz. Mass spectra were obtained on an HP 5989B mass spectrometer. Gas chromatograph-mass spectrometer (GC-MS) experiments were performed with an Agilent 6890N GC system equipped with a 5973N mass-selective detector. 2-methyl-2,4-diphenyl-2,3-dihydro-1H-1,5-benzodiazepine ( 3a ): yellow solid, m.p. 151–152 °C [152–153 °C (Mahajan et al., 2008 2008 )]; 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 1.77 (s, 3H, CH 3 ), 2.98 (d, J =12.8 Hz, 1H, CH a ), 3.15 (d, J =12.8 Hz, 1H, CH b ), 3.55 (br s, 1H, NH), 6.85–7.60 (m, 14H, ArH); IR (KBr): ν max (cm −1 ) 3325, 1632, 1595; MS (70 eV): m / z (%)=312 (18%) [M + ]. 2-methyl-2,4-di(4-methylphenyl)-2,3-dihydro-1H-1,5-benzodiazepine ( 3b ): yellow solid, m.p. 141–143 °C [142–144 °C (Kuo et al., 2006 2006 )]; 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 2.25–2.31 (m, 9H, CH 3 ), 2.95 (d, J =13.2 Hz, 1H, CH a ), 3.06 (d, J =13.2 Hz, 1H, CH b ), 3.52 (br s, 1H, NH), 6.81–7.56 (m, 12H, ArH); IR (KBr): ν max (cm −1 ) 3270, 1644, 1601; MS (70 eV): m / z (%)=340 (14%) [M + ]. 2-methyl-2,4-di(4-methoxylphenyl)-2,3-dihydro-1H-1,5-benzodiazepine ( 3c ): yellow solid, m.p. 119–120 °C [(120–121 °C (Reddy et al., 2007 2007 )]; 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 1.76 (s, 3H, CH 3 ), 2.95 (d, J =13.2 Hz, 1H, CH a ), 3.01 (d, J =13.2 Hz, 1H, CH b ), 3.78 (s, 3H, OCH 3 ), 3.88 (s, 3H, OCH 3 ), 6.77–7.51 (m, 12H, ArH); IR (KBr): ν max (cm −1 ) 3350, 1631, 1596; MS (70 eV): m / z (%)=372 (16%) [M + ]. 2-methyl-2,4-di(4-chlorophenyl)-2,3-dihydro-1H-1,5-benzodiazepine ( 3d ): yellow solid, m.p. 159–160 °C [162–163 °C (Mahajan et al., 2008 2008 )]; 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 1.75 (s, 3H, CH 3 ), 2.90 (d, J =13.2 Hz, 1H, CH a ), 3.10 (d, J =13.2 Hz, 1H, CH b ), 3.47 (br s, 1H, NH), 6.84–7.53 (m, 12H, ArH); IR (KBr): ν max (cm −1 ) 3328, 1632, 1593; MS (70 eV): m / z (%)=380 (22%) [M + ]. 2,2,4-trimethyl-2,3-dihydro-1H-1,5-benzodiaze-pine ( 3e ): yellow solid, m.p. 137–139 °C [136–137 °C (Mahajan et al., 2008 2008 )]; 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 1.34 (s, 6H, CH 3 ), 2.25 (s, 2H, CH 2 ), 2.39 (s, 3H, CH 3 ), 2.96 (br s, 1H, NH), 6.70–7.18 (m, 4H, ArH); IR (KBr): ν max (cm −1 ) 3335, 1642, 1593; MS (70 eV): m / z (%)=188 (28%) [M + ]. 2.4-diethyl-2-methyl-2,3-dihydro-1H-1,5-benzo-diazepine ( 3f ): yellow solid, m.p. 139–140 °C [140–142 °C (Mahajan et al., 2008 2008 )]; 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 0.94 (t, J =7.6 Hz, 3H, CH 3 ), 1.25 (m, 6H, CH 3 ), 1.62 (m, 2H, CH 2 ), 2.14 (d, J =12.8 Hz, 1H, CH a ), 2.23 (d, J =12.8 Hz, 1H, CH b ), 2.59 (q, J =7.2 Hz, 2H, CH 2 ), 3.08 (br s, 1H, NH), 6.69–7.26 (m, 4H, ArH); IR (KBr): ν max (cm −1 ) 3328, 1636, 1605; MS (70 eV): m / z (%)=216 (15%) [M + ]. 2-methyl-2,4-diisobutyl-2,3-dihydro-1H-1,5-benzodiazepine ( 3g ): yellow solid, m.p. 115–116 °C [117–119 °C (Mahajan et al., 2008 2008 )]; 1 H NMR (CDCl 3 , 500 Hz): δ (×10 −6 ) 0.96–1.02 (m, 12H), 1.33 (s, 3H), 1.50–1.54 (m, 2H), 1.72–1.76 (m, 1H), 2.13–2.24 (m, 3H), 2.46 (d, J =6.4 Hz, 2H), 3.14 (br s, 1H, NH), 6.68–7.26 (m, 4H, ArH); IR (KBr): ν max (cm −1 ) 3320, 1650, 1600; MS (70 eV): m / z (%)=272 (12%) [M + ]. 2,2,4-triethyl-3-methyl-2,3-dihydro-1H-1,5-benzodiazepine ( 3h ): yellow solid, m.p. 139–140 °C [142–143 °C (Mahajan et al., 2008 2008 )]; 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 0.75–1.60 (m, 15H), 2.51 (s, 3H, CH 3 ), 2.82 (q, J =6.8 Hz, 1H, CH), 3.84 (br s, 1H, NH), 6.61–7.34 (m, 4H, ArH); IR (KBr): ν max (cm −1 ) 3322, 1639, 1595; MS (70 eV): m / z (%)=244 (26%) [M + ]. 1′,2′,3′,4′,10′,11a′-hexahydrospiro[cyclohexane-1,11′-dibenzo[b,e][1,4] diazepine] ( 3i ): yellow solid, m.p. 133–134 °C [135–136 °C (Mahajan et al., 2008 2008 )]; 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 1.12–1.89 (m, 16H), 2.27–2.38 (m, 3H), 3.82 (br s, 1H, NH), 6.76–7.29 (m, 4H, ArH); IR (KBr): ν max (cm −1 ) 3290, 1640, 1600; MS (70 eV): m / z (%)=268 (23%) [M + ]. 2,3,9,10a-tetrahydro-1H-spiro[benzo[b]cyclopenta[e] [1,4]diazepine-10,1′-cyclopentane] ( 3j ): yellow solid, m.p. 135–136 °C [136–137 °C (Mahajan et al., 2008 2008 )]; 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 1.25–1.96 (m, 12H), 2.27–2.36 (m, 3H), 4.0 (br s, 1H, NH), 6.60–7.26 (m, 4H, ArH); IR (KBr): ν max (cm −1 ) 3338, 1660, 1598; MS (70 eV): m / z (%)=240 (28%) [M + ]. 2-phenyl quinoxaline ( 5a ) (Das et al., 2007 2007 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 7.51–7.58 (m, 3H), 7.74–7.82 (m, 2H), 8.12–8.21 (m, 4H), 9.34 (s, 1H); MS (70 eV): m / z (%)=206 (100%) [M + ]. 2-(4-methylphenyl)quinoxaline ( 5b ) (Das et al., 2007 2007 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 2.44 (s, 3H), 7.31 (d, J =8.0 Hz, 2H), 7.70–7.78 (m, 2H), 8.09–8.15 (m, 4H), 9.30 (s, 1H); MS (70 eV): m / z (%)=220 (100%) [M + ]. 2-(4-methoxylphenyl)quinoxaline ( 5c ) (Das et al., 2007 2007 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 3.91 (s, 3H), 7.09 (d, J =8.5 Hz, 2H), 7.70–7.79 (m, 2H), 8.09–8.19 (m, 4H), 9.30 (s, 1H); MS (70 eV): m / z (%)=236 (100%) [M + ]. 2-(2-methoxylphenyl)quinoxaline ( 5d ) (Cho and Oh, 2007 2007 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 3.91 (s, 3H), 7.07 (d, J =8.0 Hz, 2H), 7.17 (t, J =7.0 Hz, 1H), 7.47–7.51 (m, 1H), 7.74–7.79 (m, 2H), 7.89–7.91 (m, 1H), 8.12–8.18 (m, 2H), 9.34 (s, 1H); MS (70 eV): m / z (%)=236 (100%) [M + ]. 2-(3-methoxylphenyl)quinoxaline ( 5e ) (Cho and Oh, 2007 2007 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 3.95 (s, 3H), 7.08 (d, J =8.0 Hz, 2H), 7.47 (t, J =8.0 Hz, 1H), 7.74–7.81 (m, 4H), 8.12–8.18 (m, 2H), 9.32 (s, 1H); MS (70 eV): m / z (%)=236 (100%) [M + ]. 2-(4-chlorophenyl)quinoxaline ( 5f ) (Das et al., 2007 2007 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 7.54 (d, J =8.5 Hz, 2H), 7.75–7.82 (m, 2H), 8.11–8.16 (m, 4H), 9.30 (s, 1H); MS (70 eV): m / z (%)=240 (100%) [M + ]. 2-(4-bromophenyl)quinoxaline ( 5g ) (Das et al., 2007 2007 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 7.70 (d, J =8.5 Hz, 2H), 7.70–7.81 (m, 2H), 8.08–8.15 (m, 4H), 9.30 (s, 1H); MS (70 eV): m / z (%)=284 (100%) [M + ]. 2-(4-fluorophenyl)quinoxaline ( 5h ) (Das et al., 2007 2007 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 7.23–7.28 (m, 2H), 7.74–7.81 (m, 2H), 8.08–8.15 (m, 4H), 9.30 (s, 1H); MS (70 eV): m / z (%)=224 (100%) [M + ]. 2-(2-furyl)quinoxaline ( 5i ) (Das et al., 2007 2007 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 6.64 (d, J =1.5 Hz, 1H), 7.33 (t, J =3.0 Hz, 1H), 7.69–7.78 (m, 3H), 8.07–8.12 (m, 2H), 9.26 (s,1H); MS (70 eV): m / z (%)=196 (100%) [M + ]. 2-(2-thienyl)quinoxaline ( 5j ) (Peter et al., 2004 2004 ): 1 H NMR (CDCl 3 , 500 MHz): δ (×10 −6 ) 7.21 (t, J =3.5 Hz, 1H), 7.55 (d, J =4.0 Hz, 1H), 7.68–7.77 (m, 2H), 7.86 (t, J =3.0 Hz, 1H), 8.06–8.09 (m, 2H), 9.24 (s, 1H); MS (70 eV): m/z (%)=212 (100%) [M + ]. 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Non-nanogold catalyzed aerobic oxidation of secondary amines to imines 10.1631/jzus.B0900288 Project supported by the Natural Science Foundation of Zhejiang Province (No. Y407168), the Foundation of Education of Zhejiang Province (No. Z200803599), and the Opening Foundation of Zhejiang Provincial Top Key Discipline (No. 56310101634), China 2009-09-13 2009-12-31 2009-11-16 2022-01-05 Copyright © Zhejiang University and Springer-Verlag Berlin Heidelberg 2010 2010 Journal of Zhejiang University-SCIENCE B (Biomedicine and Biotechnology) 02 11