2000-2001 > Academic research: refereed > Publication in refereed journalVersion of RecordPublishe

Chan, ASC

Chen, RT

Li, Y

Wang, CZ

Yan, SK

Yuan, W

Zhao, XJ

Zhu, ZZ

2000-2001 > Academic research: refereed > Publication in refereed journalVersion of RecordPublishedVoR allowe

PolyU Institutional Repository

?????????????????????????* ?严诗楷　朱志昂　赵小菁　袁　伟　李　瑛　王传忠　陈荣悌(??????? ,????????????????? ,?? , 300071)陈新滋(?????? ,?????????? ,?? )? ?　　? L-(+ ) -??????? ,?????????? (Ⅱ )????? ,?????、???、?????????????????????? .?????????????????????????? ,??????????????????????????? ,??????、??????????????????????????? ,????????????? .???: ?????? ; ???? ; ??? ; AM 1; M M2?????: O6420　?　　???????????????????????? [1 ] ,???????????????????? .?????????????????????????????????? .????????? ,????????????? ,?????????????????????? .??????????????????????????? ,?????????? ,????????????????? .???????????????????????????????? .1　????1. 1　?????? ( A. R. ) ,?-?????? ( A. R. ) , L-(+ ) -??? ,? -?????? ,???? ( A. R. ) ,???????? [2]???? .1. 2　???????????? L-(+ ) -????? ,?????? ,?? L-(+ )-?????????? ,???? -(??? )?????????????? .???????? 1.1. 2. 1　 L-(+ ) -?????????????: ????????????????????????1?? ,? L-(+ ) -????? ,??????、???? [3 ]、?????? [ 4]、???????? [ 5]??? ,?????? .??????: C21 H26O8 S2 , C% : 53. 21( 53. 62) ; H%: 5. 66( 5. 53) ,??????? .1HNM R( 200M Hz)∶δ1. 3, 6H;δ2. 5, 6H;δ4. 1, 6H;δ7. 3, 4H;δ7. 7, 4H; [α]20D = + 4. 26°( C= 1, CH3 Cl) .? 33?　? 2? ? ? ? ? ? ? (???? ) Vo l. 33　№ 22000? 6? Acta Scientiarum Naturalium Universitatis Nankaiensis Jun. 2000?????: 1999-06-30* ??????????????????、???????? ( 29871018)、?????????????????????? 1　???????????????Fig 1　 The preparation process of 1, 4-ditosyl-2, 3-O-isopropylidene-threitol1. 2. 2　?-(??? )?????????????: ? -(??? )????????????????? 2?? .???? [6 ]?????? -(???? )??????-(??? )???? ,????????:C48H38N4O4 , C% : 78. 01( 78. 45) ; H% : 5. 37( 5. 22) ; N% : 7. 44( 7. 64) .???????? [4]???? ,???????????? ,?? 2,????????? ,?????????? ,???? [4 ] ,?????????????? ,?????????? ,???????????? ,??????????:C58 C50N4O8· 4H2O, C%: 69. 49( 69. 46) ; H%: 5. 36( 5. 79) ; N% : 5. 28( 5. 59) , Uv-v is( CH2 Cl2 ):λ407( sh )、426 ( So ret )、 490( sh)、 522、 558、 604、 664nm;???? (?? )?????? ,??????? ChiralZnT PP,??????: ZnC58 H48N4O8· 4CH3OH, C% : 66. 35 ( 66. 34) ; H%: 7. 16 ( 5. 75) ; N% : 4. 20( 4. 99) ,??????? .? 2　?-(??? )???????????????Fig 2　 The preparation process of T(OH)TPP and chiral ZnTPP1. 3　?????????????????? Shimadzu UV-160????????? ,???????? ,???????? 0. 5nm,????? 100nm /min,????? 400～ 500nm ,???? 1cm????????? .1. 4　????????? AM1???? CambridgeSo ft??? CS Chem3D( R) Version 4. 0 Fo r Window s 95 and Window s N T??·2· 　? ? ? ? ? ? (????? ) ? 33?? ,??????????????? MM2?? ,????????????????? MO PAC( AM 1)???? ,? Pentium200 /64M RAM??????? ,??????? ( RM S)? 0. 1.1. 5　?????????? ( P)??? ( L)?????????????????????:P+ n LKPLn ( 1)?? K????????? , L?????? ,n???????????? .?????????:K=[ PLn ]e[ P ]e [L ]ne?????“ e”?????? .?? Lamber-beer?? ,???????????????????? ,?????? [8 ]:ln(A∞ - AeAe- A0)= n lnCL+ lnK ( 2)???????? , ( 2)??????:A0Ae- A0=EKCnL+ E ( 3)??????? Ae????????????? ,??????????????? n?????K .???????? Δr Hθm? Δr Sθm????????? ,??? Van 't Hof f??lnKθ= - Δr HθmRT+Δr SθmR( 4)? 3　?? ZnPP????? Im???????Fig 3　 Spectral change onthe addition of Imto chiral ZnTPP?? Kθ= K / ( mol- 1· dm3 ) ,?????????????????????????? ,???????????????????? .2　?????2. 1　??????????????????????????????? 400～ 500nm?????????????? .??????? ,???????????????????????? ,?? 3,???????????????????????? ,???????????? 429nm? ,????????? ,??????????? ,??? 5nm?????????? .?????????????? .2. 2　????????????????????????????????????????????????? .??? ( 2)?????? n,??? ( 3)?????????K ,?? 4?? ,?? Van 't Hof f?? ,? lnKθ～ 1 /T ?? (? 5) ,?????( 1)?????????????? ,??????????????????? 1.??????????? 1,?????????????: K HOCH2-MeIm>KMeIm> K Im , K Zn TPP> K chiral ZnTPP.2. 3　??????????????????????????? MM2??????????????????????? ,?????????? AM1??????? ,?????????????? .???????????????????? ,???、??????????? 429. 5951k J·mol- 1? 472. 3030k J· mol- 1 ,????????? .???????????? ,???????????? ,?????? ,????????????? .·3·　? 2? ????:?????????????????????????　　? 4　?? ZnTPP～ HOCH2-MeIm?????-A0 /(Ae-A0 )? 1 /C??　　 Fig 4　 Plot of-A0 /(Ae-A0 ) vs 1 /C of chiral ZnTPP withHOCH2-MeIm　　? 5　?? ZnTPP?????????? lnKθ? 1 /T??　　 Fig 5　 Plot of lnKθ vs 1 /T of chiral ZnTPP with threeligands? 1　???????????Table 1　 Thermodynamic constants of all reactions??? ???? K /( dm3· mo l- 1 ) Δr Hθm Δr Sθmzinc imida zo le 15℃ 20℃ 25℃ 30℃ /( K J· mol- 1 ) /( J· mo l- 1K- 1 ) nproph yrins deriv ativ esHOCH2-MeIm 87318. 10 53662. 81 3642. 13 23585. 83 - 41. 536 - 58. 284 1. 023ZnTPP M eIm 26071. 86 19697. 04 16181. 79 12901. 61 - 30. 214 - 27. 003 1. 212Im 18917. 88 15049. 04 12145. 62 10172. 38 - 27. 587 - 19. 808 1. 061chiral HOCH2-MeIM 31249. 24 21910. 24 17196. 77 13069. 77 - 62. 681 - 123. 044 1. 072ZnTPP M eIm 11315. 66 9841. 20 7640. 04 6148. 48 - 33. 532 - 31. 952 1. 069Im 9157. 83 7728. 43 6286. 88 5207. 00 - 30. 169 - 22. 890 1. 038　　?????? MM2?????????? 6?? .?????????????? ,??? AM1?? ,????????????????????? N?????? ,?? 2?? ,??????:HO CH2-MeIm> MeIm> Im ,??????? K HOCH2-MeIm> KMeIm> K Im??????? .? 6　?????????Fig 6　 The optimized conf igures of three ligands2. 4　????????????????? 1?????? ,??????????????? ,???? ,????????? .??????????????????????? ,???????????? d??????? π???????????????????? ,Δr Hθm??? ,???????????????? ,Δr Sθm??? ,?? Van 't Ho ff?? ,???????? K??? ,???? Δr Hθm???????? ,???????????? .?? 5??????? ,???????????????? , HO CH2-MeIm??????·4· 　? ? ? ? ? ? (????? ) ? 33?? ,???????????????????? Δr Hθm? Δr Sθm .? 2　???? N???????Table 2　 The dif ference of N atom 's nucleophilication of three ligands???? lig ands HOCH2-M eIm M eIm Im????? atom ne t char ges - 0. 1517 - 0. 1503 - 0. 1421????? electr ostatic po tential cha rg es - 0. 5511 - 0. 5275 - 0. 50082. 5　????????????????????????????? 7.?? 1???? ,????????? ,???????????????? . HO CH2-M eIm?? , K Zn TPP> K chiral Zn TPP????????????????? ,??????????????? ,???????????????????? ZnT PP??? K? .??????????????? ,??????? ,???????????????????? ,???????????????????????????????? ,?????????????????????? ,?????????????????????? ,????????????? ,????????????? Zn TPP?? .? 7　???????Fig 6　 The structure of host and guest molecule2. 6　????????????????? 1? ,???????????????????????????? .??????????????????????????????? , K HOCH2-MeIm> KMeIm> K Im??????????? .HO CH2? Me??????????? N?????????? ,? 2????????????????????: K HOCH2-MeIm> KMeIm> K Im ,???????? ,?????????????????? .? ? ? ?　 1　 Naruta Y , Tani F, Ishihara N et al . Ca ta ly tic and asymme tric epoxida tion o f olefins with iron complexes of “ tw in-cor onet” po rphy rins, a mechanistic insight into the sty rene deriva tiv es. J Am chem Soc, 1991, 113: 6865～ 6872Collman J P, Zhang X, Lee V Jet al. Regioselectiv e and enantio selectiv e epox idation ca taly zed by metallopo rphyins.Science , 1993, 261: 1404～ 1411Groves J T , V iski P. Asymme try hydroxy la tion, expox idation and sulfo xida tion cataly zed by vaucted binaph th ylmetalloporphy rins. J Org Chem , 1990, 55( 11): 3628～ 3634　 2　 [? ]?? D D,???? W L F,?? D R? ,??? . ???????????? . ??? . ??: ??????? , 1987　 3　 Meskens F A J. Methods fo r the prepara tion o f acetals from alcoho ls or o xiranes and cabonyl compounds. Synthesis,1981, 501～ 502Al-Hakim A H, Haines A H, Mor ley C. Synth esis of 1, 2-O-isopr opylidene-L-thr eito l and its conve rsion to ( R) -1, 2-O-isopropylideneg ly cerao l. Synthesis, 1985, 207～ 209　 4　 Soai K, Oyamada H, Ockawa A. Sodium borohydride-t-buty l alcohol-methano l as an efficient system fo r the·5·　? 2? ????:?????????????????????????selec tiv e reduction of ester s. Syn Comm , 1982, 12( 6): 463～ 473　 5　 Frech et J M J, Ketty J, Sher rinton D C. Some novel po lymer-suppo r ted optically activ e phase transfer ca ta ly sts: 1Synthesis. Polymers, 1984, 25: 1491～ 1504　 6　 Mom entean M . Both-fa ces hindered porphy rins. Pa rt I. Synthesis and cha racteriza tion o f basked-handle po rphyrinsand their iron complexes. J Chem Soc, Perk in Trans I , 1983, 189～ 196　 7　 Co llman J P, V irigil J L , Kellen-Yuan C J et al. Thr eito l-strapped Manganese po rphy rins ad enantio selectiv eepox idation ca talysts of unfunctionalized o lefins. J Am Chem Soc. 1995, 117: 692～ 703　 8 　 Ma Y X, Zhu Z A, Ch en R T . Thermodynamic o f ax ia l co o rdina tion reaction o f par a-substitutedte rapylpo rphy rinatoir on (Ⅲ ) ch lo ride. Thermochimica Acta , 1990, 171: 223～ 228SYNT HESIS OF CHIRAL ZINC PORPHYRINAND ITS T HERMODYNAM IC STUDY OF COORDIN AT IONREACT IONS WITH SUBST ITU TED IM IDAZOLESYan Shikai, Zhu Zhiang , Zhao Xiaojing , Yuan Wei , Li Ying, Wang Chuanzhong , Chen Rongti(Department of Chemistry , State Key Laboratory of Elemental Organic Chemistry ,N ankai University , Tianjin , 300071)Alber t S. C. Chan(Department of Applied Biology & Chemical Technology , The Hongkong Poly technic University , Hongkong )Abstract　　 Sta rted o ff wi th the normal chi ral material, L-(+ ) -ta rtaric acid, a series o f novel chiralZinc (Ⅱ ) porphyrin is prepared, and Elements analysis, NM R, Uv-vis and Po la rizationanalysis giv e the characterization. A thermodynamic study has been carried out for the axialcoo rdina tion reactions betw een chiral po rphy rin and some imida zo le-like lig ands. Elect ronicimplica tion is found to be an impo rtant factor in i ts thermodynamics, furthermore, wi thmolecular mechanics method, MM 2, and semi-empirical method in Quantum Chemist ry ,AM1, configura tion optimiza tion and o ther calculation have been ca rried out on porphyrins andlig ands, who se resul ts are inline w ith the experiments.Key words: chira l metallopo rphy rin; axial coo rdination; thermodynamics; AM 1; MM2·6· 　? ? ? ? ? ? (????? ) ? 33?

Synthesis of chiral zinc porphyrin and its thermodynamic study of coordination reactions with substituted imidazoles

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