Biomimetic Based Applications Part 2 doc

2 Biomimetic Oxidation of Hydrocarbons with Air over Metalloporphyrins !"#$%&'()*%&'+(,*%&'(-*"(%&.(/%&012&'(!"#3( School of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, Hunan, P. R. China 1. 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Biomimetic oxidation of C-H of alkanes _202&6(G#;U(#&(0%6%?:6*0(1:.;#5:?%6*#&("=*&'(>26%??#A#;A1:;*&7<%=2.(#5*.%6*#&(=:=62>=(*=( >%*&?:($#0"=2.(#&(/`8(<#&.=(#$(%?U%&2F(T($2G(;2=2%;01(';#"A=(;2A#;62.(%(0%6%?:6*0(=:=62>( 0#&=*=6*&'( #$( >#&#>26%??#A#;A1:;*&( %&.( >#?20"?%;( #5:'2&BYO7YPEF( a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iomimetic 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Biomimetic oxidation of alkenes S&(612( 2?.(#$( #?2&(#5*.%6*#&=( G*61(>#?20"?%;(#5:'2&( 0%6%?:M2.(<:( (>26%??#A#;A1:;*&=+( 612( 0%6%?:6*0( =:=62>( >26%??#A#;A1:;*&=7J X 7^8 Q 7( G2;2( .2@2?#A2.BDREF( S&( 61*=( 0%6%?:6*0( =:=62>+( =#.*">(<#;#1:.;*.2(IK%^8 Q L("=2.(%=( ;2."06%&6(G%=( 2==2&6*%?($#;( #5:'2&%6*#&(#$(#?2&=BDDEF( -%62?:+( =#>2( A%A2;=( ;2A#;62.( 612( %2;#<*0( #5*.%6*#&( #$( #?2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iomimetic Oxidation of Hydrocarbons with Air over Metalloporphyrins 37 3.1 Biomimetic oxidation of C-H 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XC( NR( QFW( OFNkCW Q ( 4%<?2(RF(s$$206(#$(0%6%?:=6(0#&02&6;%6*#&(#&(0:0?#1252&2(#5*.%6*#&(;2%06*#&( 412( 0#&@2;=*#&( #$( 0:0?#1252&2( G%=( "A( 6#( XC( e+(612(=2?206*@*6:(#$(0:0?#1252&#&2(;2%012.(( NRe( "&.2;( 612( #A6*>">( 0#&.*6*#&=( #$( WFQ( ZV%+( OW( o/( %&.( XFYkCW 7R >#?H-( 0#<%?6( 626;%A12&:?A#;A1:;*&F( 3.2 Biomimetic oxidation of C=C of styrene S&(XWWD+(j2BNRE(;2A#;62.(%(&#@2?(%2;#<*0(#5*.%6*@2(0?2%@%'2(#$(/9/(.#"<?2(<#&.=(#$(=6:;2&2( 0%6%?:M2.(<:(=*>A?2(>%&'%&2=2(A#;A1:;*&I\012>2(DLF(( ( manganese porphyrin T,P + H O O +otherproducts ( \012>2(DF(T2;#<*0(#5*.%6*#&(#$((=6:;2&2(<:(>26%??#A#;A1:;*&( a&.2;( 612( 0%6%?:=*=( #$( 01?#;#I626;%A12&:?A#;A1*&%6#L>%&'%&2=2+( 612( #5*.%6*@2( 0?2%@%'2( #$( 612( 0%;<#&70%;<#&( .#"<?2( <#&.( #$( 612( =6:;2&2( G*61( %*;( :*2?.=( 612( >%*&( A;#."06( <2&M%?.21:.2F( 412( ;2="?6=( =1#G( 61%6( 612( #5*.%6*@2( 0?2%@%'2( %&.( 612( 2A#5*.%6*#&( #$( 612( =6:;2&2(.#"<?2(<#&.(%;2(612(0#>A26*6*#&(;2%06*#&=(*&(612(=6:;2&27>%&'%&2=2(A#;A1:;*&7%*;( =:=62>F(412(;2%06*#&(62>A2;%6";2(.20*.2.(612(A;#."06(.*=6;*<"6*#&F(a&.2;(612(0#&.*6*#&=(#$( WFQ( ZV%( %*;( %&.( YW( AA>( #$( 01?#;#I626;%A12&:?A#;A1*&%6#L7( >%&'%&2=2+( 612( =6:;2&2( 0#&@2;=*#&(G%=(XWFWe(%&.(612(=2?206*@*6:(#$(<2&M%?.21:.2(%&.(=6:;2&2(#5*.2(G%=(OCFNe(%&.( CXFNe( ;2=A206*@2?:( G12&( 612( ;2%06*#&( 62>A2;%6";2( G%=( CCW( o/F( \6:;2&2( 0#&@2;=*#&( G%=( PXFRe( %&.( 612( =2?206*@*6:( #$( <2&M%?.21:.2(%&.(=6:;2&2(#5*.2(G%=(QOFCe(%&.(QCFXe( ;2=A206*@2?:(G12&(612(;2%06*#&(62>A2;%6";2(G%=(CXW(o/F( 3.3 Biomimetic oxidation of C=C and allylic CEH bonds in Į-pinene ǂ7A*&2&2(*=(612(=*&'?2(?%;'2=6(;2&2G%<?2(62;A2&2(*&(&%6";2(%&.(%&(*>A#;6%&6(*&."=6;*%?(;%G( >%62;*%?( *&( 612( 62;A2&2( *&."=6;:F( j*61( #5*.%6*#&+( *=#>2;*M%6*#&+( %&.( 1:.;#'2&%6*#&+( ǂ7 A*&2&2( 0%&( A;#."02( %( @%;*26:( #$( *>A#;6%&6( A;#."06=F( 412( ǂ7A*&2&2( 2A#5*.2( 1%=( ';2%6( *&."=6;*%?(@%?"2F(j2BNDE(;2A#;62.(=*>A?2(>26%??#A#;A1:;*&=I4VVZ&/?+(4VV/#/?+(4VV[2/?+( 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T(p-Cl)PPMnCl-Co(OAc) 2 + O2 H 3C Acetic acid T,P COOH HOOC PTA COOH + OHC 4-CBA TPA Scheme 13 Aerobic oxidation of p-toluic acid by metalloporphyrin-Co(OAc )2 in acetic acid COOH COOH COOH T(p-Cl)PPMnCl,O 2 CH 3 a Co 2+ CH 2OH -OH - b COOH c CH 3 COOH COOH O2 Co 3+ COOH Co 2+ COOH [O] H+ CH 2O CH 2 CH 2OO CHO COOH -1 /2 O 2 Scheme 14 Preliminary mechanism of co-catalysis between T(p-Cl)PPMnCl and Co(OAc )2 in the... Catalyzed by Cytochrome P450 Enzymes, Chem Rev, 20 04, 104, 3947 [22 ] V B Urlacher and S Eiben, Cytochrome P450 Monooxygenases: Perspectives for Synthetic Application, Trends Biotechnol, 20 06, 24 , 324 [23 ] D Mansuy, Biocatalysis and Substrate Chemodiversity: Adaptation of Aerobic Living Organisms to Their Chemical Environment, Catal Today, 20 08, 138, 2 [24 ] B Meunier, Biomimetic Oxidations Catalyzed by Transition...41 Biomimetic Oxidation of Hydrocarbons with Air over Metalloporphyrins Selectivity(mol %) Benzyl Benzoic Conversion mol% Benzaldehyde alcohol acid Co(II)TPP 33 27 39 8.9 Co(OAc )2 29 20 50 2. 9 Catalyst Turnover number mol/mol 24 275 3 125 Table 9 Comparison of aerobic oxidation of toluene catalyzed by Co(II)TPP and Co(OAc )2 The further investigationresulted that... 37, 21 80 [ 12] A Corma and H Garca, Lewis Acids as Catalysts in Oxidation Reactions: From Homogeneous to Heterogeneous Systems, Chem Rev, 20 02, 1 02, 3837 [13] B Limberg, The Role of Radicals in Metal-Assisted Oxygenation Reactions, Angew Chem Int Ed, 20 03, 42, 59 32 [14] Q H Xia, H Q Ge, C Ye, Z M Liu and K X Su, Advances in Homogeneous and Heterogeneous Catalytic Asymmetric Epoxidation, Chem Rev, 20 05,... Chem Int Ed Engl, 20 00, 39, 23 10 [50] R Raja, G Sankar and J M Thomas, Powerful Redox Molecular Sieve Catalysts for the Selective Oxidation of Cyclohexane in Air, J Am Chem.Soc, 1999, 121 , 11 926 [51] E L Pires, M Wallau and U Schuchardt, Selective Oxidation of Cyclohexane over Rare Earth Exchanged Zeolite Y, Stud Surf Sci Catal, 1997, 110, 1 025 54 Biomimetic Based Applications [ 52] E L Pires, M Wallau... elsewhere (Shteinman, 20 01; Watanabe, 20 01; Sligar et al., 20 05) Monooxygenases require a metal center (transition metal ions, predominantly iron and copper) and two electrons to reductively cleave atmospheric dioxygen, producing only a single water molecule in the process while saving the second atom for substrate functionalization and formal oxidation: RH O2 2 H ROH H2O 64 Biomimetic Based Applications In... at al., 20 00, Meunier, 20 00; Simões et al., 20 06), and numerous classes of substrates have been given in transformation including pre- and post-emergence herbicides (Chauhan & Kumari, 20 07), amino acids (Mukherjee & Ray, 20 07), monoterpenes such as: geraniol, nerol, limonene, pinene, -terpinene, 1,8-cineole, carvacrol, thymol, and cymene (Martins et al., 20 01; Maraval et al., 20 02, Guo et al., 20 05;... College Press, London, 20 00 [25 ] R V Eldik and J Reedijk, Homogeneous Biomimetic Oxidation Catalysis, Adv Inorg Chem, Elsevier, Amsterdam, 20 06, 58 [26 ] P Gamez, P G Aubel, W L Driessen and J Reedijk, Homogeneous Bio-inspired Copper-Catalyzed Oxidation Reactions, Chem Soc Rev, 20 01, 30, 376 [27 ] R A Sheldon, D Marcel, Metalloporphyrins in Catalytic Oxidations, New York, 1994 [28 ] I T Groves, T E Nemo . <:(/V7QRWBYR+PCE(I 12& gt ;2( CDL+( 61 ;22 ( .*$ $2; 2&6( =A20 *2= (1% @2( < ;22 &( 0#&=* .2; 2.(%=( A#==*< ?2( %06* @2( #5*.%&6=BXEm( #& ;2( A ;2= 2&6*&'(%( &"0 ?2# A1*?*0( 01%;%0 62; +(%(A2;#5:(=A20 *2= (I.L+(#& ;2( G*61 (2? 206;#A1*?*0(01%;%0 62; +(%(*;#&ISpL(#5#(A#;A1:;*&(A7 0%6*#&(;%.*0%?(*& 62; > ;2. *% 62( INL(=*>*?%;(6#(6 12( /#>A#"&.(S(I/A.(SL(#$(1#; =2; %.*=1(A2;#5*.% =2+ ( %&.(6 12( ?%=6(G*61(<#61(&"0 ?2# A1*?*0(%&. (2? 206;#A1*?*0(01%;%0 62; +(%(1:.;#A2;#5:(=A20 *2= (I [2 SSS 7 JJ8I_L+(. =1#G2.( 61%6(0:0?# 125 %&#& ;2( : *2? .(*&0 ;2% =2. 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