2002-2003 > Academic research: refereed > Publication in refereed journalVersion of RecordPublishe

Chan, ASC

Chen, XM

Fan, QH

Liu, GG

Yang, XQ

2002-2003 > Academic research: refereed > Publication in refereed journalVersion of RecordPublishedVoR allowe

PolyU Institutional Repository

?????????????????????????范青华1 , 杨夕强1 , 刘国华1 , 陈晓闽1 , 陈新滋2( 1. ???????????????? , ?? 100080;2. ???????????????? , ?? )??　?????????????? ( BINOL )?????????????????????????? . (R ) -2, 2′-??? -1, 1′-?? -3, 3′-?????????? Frechet????????????? , ??????? 0～ 3???????? , ? 1 HNM R, IR? M ALDI-TOF????????? . ????????? Ti( OPri ) 4?????????????????????????????????? , ?????????????????????????? . ?????????? , ??????????????????????? .???　 1, 1-?? -2-? ; ??????? ; ??????????　 O625. 23　　　　?????　 A　　　　????　 0251-0790( 2003) 02-0274-04????: 2001-12-03.????: ???????? (???: 29904009? 20132010)?? .?????: ??? ( 1966??? ) ,? , ?? , ???? , ????????? . E-mai l: f anqh@ infoc3. icas. ac. cn?????????????????????????? , ??????????? [ 1] . ?? ,??????????????????????????????????????? , ??????? [2～ 4 ] . ?? , ?????????? , ??????“???? -????”???????????????? [5, 6 ] . ?? , ???????????????、????????????????????????????? [7 ] . ?? , ?????????????? BIN AP[ 6]? BINOL[8 ]????? , ??????????????????? , ????????“??????”?? . ?????? BINOL??? Ti( O Pri ) 4????????????????????????? , ???e.e.??????????????? , ????“??????”?? .??????????????? 3, 3′-???????????????????? , ????????? BINOL????????? , ???????????????? BINOL??? , ?????????????????????? , ????????????????????????? .1　?????1. 1　 ?????????? Scheme 1?? .?? [9 ]???????? BINO L???? , ?????????????? 3, 3′-?? 6, 6′-? , ???? 3, 3′-?????? BINOL??? ( R) -1????? , ?????????????????? , ??????????????????? . ??? ( R ) -1???? [10 ]???? . ?????????? 2????? Frechet????? [11 ]????? ( Gabriel)?????? . ???(R ) -1? SOCl2?????? , ?????? 2????????????????? (R ) -3, ???????? 3? MALDI TO F????????????? 1.Vol. 24 高 等 学 校 化 学 学 报 　 No. 2　2 0 0 3? 2? 　　 　　　　　 CHEMICAL JOURNAL OF CHINESE UN IVERSITIES　　　　　　　　　 274～ 277　Scheme 1　 Route of synthesis???????? 3?? 1H NMR, IR? MADALI-TOF-M S?? . ??????? 3???????????? 1H NMR?? , ????????? BINOL???????????? C2??? . ?? 1???? , ?????? BINOL?????????????? , ???????? 3?????????? . ??? 3???????????? (? 1)???? , ?????????? ,????? [T]D?? , ???????????????? , ???????? BINO L?????????? BINO L?????????? .Table 1　 Characterizat ion of ch iral dendritic BINOLs (R )-3Compd. Yield (% ) Calcd. massMass found[M+ Na ]+[T]20D(c 1. 0, CHCl3)Molar rotation(R ) -3a 60. 0 976. 37 999. 69 + 52. 0 508. 1( R )-3b 75. 0 1 824. 71 1 849. 36 + 22. 0 401. 8(R ) -3c 72. 0 3 521. 38 3 545. 65 + 10. 0 352. 41. 2　 ?? 3?????????????????????????????????????????? , ???????????????????? , ??????????? ,??????? , ?????? 20% (???? )?????? 80% (???? )??????? , ???????? 7 h. ??????? 2.Tabl e 2　 Asymmetric addition of diethyl zinc to aldehydes catalyzed by the dendr iticBINOL l igands 3 in the presence of Ti(OPri )4Entry Ligand Ald ehyde Conv. (% ) e. e. (% ) Ent ry Ligand Aldeh yd e Conv. (% ) e. e. (% )1 3a PhCHO 97 71. 7( 73. 7[8 ]) 6 3c 2-Cl-PhCHO > 99 72. 82 3b PhCHO 99 65. 8( 53. 8[8 ]) 7 3a 3-Cl-PhCHO > 99 51. 93 3c PhCHO > 99 70. 1( 52. 2[8 ]) 8 3b 3-Cl-PhCHO > 99 46. 54 3a 2-Cl-PhCHO > 99 67. 6 9 3c 3-Cl-PhCHO 98 45. 75 3b 2-Cl-PhCHO > 99 69. 2　　?? 2???? , ??????????? 3? Ti ( OPri ) 4?????????????????????????????? . ????????????????????? , ??????? , ??? e. e.???????? , ????????????? , ??? e. e.?????? (??2) . ?????????????????? 3, 3′-?????????? BINOL???????????? [ 8] , ????????????????????????? . ?????????????? , ???????????? , ?????????????? ; ???? , ????????275No. 2 范青华等: 新型树状结构手性联二萘酚衍生物的合成及催化性能的研究 　　　? N— H????? Ti? Zn??????? , ?????????????????? . ???????????????? , ??????????????????????? .?? , ??? BINOL??????? 3, 3′-??????? , ???????????? BINO L??? , ????????????????????????????????????????????? . ???????????????????????????? , ????????????? , ??????? , ????????????????? .2　????2. 1　?????Bruker IFS 25?????????? ; Bruker DM X300( 300 M Hz)?????? ; AA-10R??????? ; Varian 6000????? [SupelcoU-Dex 120 GLC( 0. 25 mm× 30 m)????? ].??????????? , ??????????????? . ????????????? .????????????? .2. 2　??? (R )-3a～ (R )-3c???? 50 mL????? ,?? 0. 3 g ( 0. 8 mmol) ( R) -1, 10 m L???? , ???? 4 h, ?? , ???????? . ?? 5 mL???? , ?? 0℃ , ?? 1. 535 g ( 4. 8 mmol)??? 2(n= 0)? 5 mL?????? , ????? , ?? 0. 5 h. ???? 5%???????? , ??????? 3? , ??10 mL, ????? , ?????????、 ????????? , ???????? ; ??? [V (??? )∶ V (???? )= 1∶ 1 ]?????? (R ) -3a 0. 485 g, ?? 60% . m. p. 82～ 83℃ ; [T]20D= + 52(c 1, CHCl3 ) ; IR( KBr, ν~ /cm- 1 ): 3 372, 3 080, 2 863, 1 651, 1 595, 1 532, 1 452, 1 296, 1 262,1 152, 1 028, 802, 738; 1 H NM R( CDCl3 ) , W: 11. 9( s, 2H) , 8. 07( s, 2H, BINOL— H) , 7. 68( d, J=7. 7 Hz, 2H, BINO L— H) , 7. 39～ 7. 21( m, 26H, Ar— H ) , 7. 09( d, J= 8. 04 Hz, 2H, BINOL— H) ,6. 61～ 6. 55( m , 6H, Ar— H) , 4. 99( s, 8H, Ph— CH2 ) , 4. 60( dd, J 1= 5. 3 Hz, J 2= 14. 3 Hz, 2H,Ph— CH2 ) , 4. 52( dd, J1= 5. 3 Hz, J2= 14. 2 Hz, 2H, Ph— CH2 ) ; M ALDI-TOF-M S, m /z: 999. 69[M+ Na ]+ .??? ( R) -3b?????? , ?? 75% . m. p. 80～ 81℃ ; [T]20D= + 22(c 1, CHCl3 ) ; IR( KBr,ν~ /cm- 1 ): 3 356, 3 033, 2 873, 1 650, 1 595, 1 529, 1 451, 1 295, 1 152, 1 053, 831, 737; 1 H NMR( CDCl3 ) , W: 12. 1( s, 2H) , 8. 05 ( s, 2H, BINOL— H) , 7. 63 ( d, J = 7. 8 Hz, 2H, BINOL— H) ,7. 40～ 7. 29 ( m, 40H, Ar— H ) , 7. 22～ 7. 09 ( m , 8H, Ar— H) , 6. 69～ 6. 58 ( m , 18H, Ar— H) ,5. 01～ 4. 92 ( m , 24H, Ph— CH2 ) , 4. 53～ 4. 49( dd, J1 = 5. 3 Hz, J 2= 14. 3 Hz, 2H, Ph— CH2 ) ,4. 77～ 4. 70(dd, J 1= 5. 3 Hz, J 2= 14. 3 Hz, 2H, Ph— CH2 ) ; M ALDI-TOF-M S, m /z: 1 849. 36 [M+Na ]+ .??? ( R ) -3c?????? , ?? 72% . m. p. 78～ 80℃ ; [T]20D= + 10(c 1, CHCl3 ) ; IR( KBr,ν~ /cm- 1 ): 3 380, 3 031, 2 870, 1 726 1 596, 1 448, 1 297, 1 151, 1 044, 829, 738; 1H NMR( CDCl3 ) ,W: 12. 0( s, 2H) , 8. 05( s, 2H) , 7. 68( s, 2H, BINOL— H) , 7. 43～ 7. 10( m, 88H, Ar— H) , 6. 70～6. 52( m, 42H, Ar— H) , 5. 07, 4. 99, 4. 95( s, 56H, Ph— CH2 ) , 4. 60(dd, J 1= 5. 4 Hz, J 2= 14. 4 Hz,2H, Ph— CH2 ) , 4. 48 ( dd, J 1 = 5. 4 Hz, J2 = 14. 4 Hz, 2H, Ph— CH2 ) ; M ALDI-TOF-M S, m /z:3 545. 65[M+ Na ]+.2. 3　???????????? , ???? 3a( 24. 4 mg, 0. 025 mmol )?? 1 mL??? , 10 min??? 40μLTi ( OPri) 4 ( 0. 10 mmol) , ????? 10 min, ?? 0. 375 mL( 1. 0 mol /L)?????????? , ???? 10 min; ????? 0℃ , ?? 13μL( 0. 125 mmol) ???? , ?? 7 h; ????? , ??2. 0 mL( 1. 0 mol /L)????????? , ??????? , ????? , ???????????、??????????? , ??????????? , ?? , ?? , ?????????? 1-??-1-276　　　 高 等 学 校 化 学 学 报 Vol. 24????? . ??????????? ( Chiral BETA DEXTM 120, 0. 25 mm× 30 m )????? e. e.? . ????????????? R?? .?　?　?　?[ 1 ]　 Fan Q. H. , Li Y. M. , Chan A. S. C. . Ch em. Rev. [ J] , 2002, 102: 3 385— 3 466[ 2 ]　 Yang X. W. , Su W. , Liu D. X. et al . . Tetrah edron [ J] , 2000, 56: 3 511— 3 516[ 3 ]　W ANG Heng-Sh an(??? ) , SU Wu(?　? ) , LIU Da-Xue(??? ) et al . . Chem. J. Chinese Universi ties(???????? )[ J ] , 2000, 21( 10): 1 524— 1 526[ 4 ]　 Hu J. , Zhao G. , Yang G. et al . . J. Org. Chem. [ J ] , 2001, 66: 303— 304[ 5 ]　 Fan Q. H. , Ren C. Y. , Yeung C. H. et al. . J. Am. Chem. Soc. [ J] , 1999, 121: 7 407— 7 408[ 6 ]　 Fan Q. H. , Ch en Y. M . , Chen X. M . et al. . Ch em. Commun. [ J] , 2000: 789— 790[ 7 ]　 As truc D. , Chardac F. . Chem. Rev. [ J] , 2001, 101: 2 991— 3 023[ 8 ]　 Fan Q. H. , Liu G. H. , Chen X. M . et al. . Tet rah edron: Asymmetry [ J] , 2001, 12: 1 559— 1 565[ 9 ]　 Pu L. . Ch em. Rev. [ J] , 1998, 98: 2 405— 2 494[10 ]　 Kitajima H. , Ito K. , Aoki Y. et al . . Bull. Chem. Soc. Jpn. [ J] , 1997, 70: 207— 217[11 ]　 Haw ker C. J. , Fré ch et J. M . J. . J. Am. Chem. Soc. [ J ] , 1990, 112: 7 638— 7 647Synthesis of New Dendritic Chiral BINOL Ligands and TheirApplications in Enantioselective Lewis Acid CatalyzedAddition of Diethyl zinc to AldehydesFAN Qing-Hua1*, Y ANG Xi-Qiang1, L IU Guo-Hua1, CHEN Xiao-Min1, Albert S. C. Chan2( 1. Center for Molecular Science, Institute of Chemistry , Chinese Academy of Sciences,Beijing 100080, China; 2. Open Laborator y of Chirotechnolog y and Department of Applied Biologyand Chemical Technology , Hong Kong , China)Abstract　 The series of new dendritic chi ral BINOL ligands( 3) w ere synthesized by condensation reactionof (R ) -2, 2′-dihydroxy-1, 1′-binaphthyl-3, 3′-dicarboxylic acid( 1) and Fré chet-type poly (aryl ether) den-drons( 2) wi th an amino g roup at the focal point in moderate reaction yields. All ligands w ere characterizedby1H NMR, IR and MALDI-TOF-M S spect ra, which clearly demonst rated the fo rmation of monodis-persed dendri tic BINOLs. The titanium complexes of these dendri tic lig ands obtained by mixing ( 3) wi thTi ( OPri ) 4 in dry toluene w ere found to be efficient catalysts in asymmetric addi tion of diethylzinc to alde-hydes. The size of the dendritic w edges did not significantly inf luence the enantioselectivity of the cataly st.Most interesting ly , w hen ortho-chlorobenzaldehyde was used as subst rate, w e found that enantioselectivityincreased slightly with increasing generation of the dendrimers.Keywords　 1, 1′-BINOL; Chiral dendrimer; Asymmetric catalysis( Ed. : H, J, Z)277No. 2 范青华等: 新型树状结构手性联二萘酚衍生物的合成及催化性能的研究 　　　

Synthesis of new dendritic chiral binol ligands and their applications in enantioselective lewis acid catalyzed addition of diethylzinc to aldehydes

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