Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Chiral Carbonyl Iron Systems

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1 , ACTA CHIMICA SINICA Vol 62, 2004 No 18, Ξ Ξ ( ) [ Et 3 NH] + [ HFe 3 (CO) 11 ] - 1,12, 98 % Fe 3 (CO) 12, Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Chiral Carbonyl Iron Systems CHEN, Jian2Shan CHEN, Ling2Ling XING, Yan CHEN, Gui SHEN, Wei2Yi DONG, Zhen2Rong LI, Yan2Yun GAO, Jing2Xing Ξ ( Department of Chemistry, State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen ) Abstract Chiral carbonyl iron systems have seldom been used in asymmetric transfer hydrogenation of aromatic ketones In this study, new chiral iron catalytic systems were synthesized in situ from different carbonyl iron complexes with chiral diaminodiphosphine ligands, respectively asymmetric transfer hydrogenation of various aromatic ketones under mild conditions These catalytic systems have been used for the The results indicated that trinuclear iron complexes were the best systems for the reactions When the [ Et 3 NH] + [ HFe 3 (CO) 11 ] - as catalyst was used for asymmetric reduction of 1,12diphenylacetone, high enantioselectivity up to 98 % was achieved Monitoring the reaction in situ by infrared spectroscopy, it could be conjectured that the carbonyl iron cluster Fe 3 (CO) 12 kept its trinuclear skeleton unchanged during the catalytic reaction Keywords carbonyl iron, chiral diaminodiphosphine ligand, aromatic ketone, asymmetric transfer hydrogenation [1,2],, i2proh/ KOH [9 12], HCOOH/ Et 3 N,, PN, NPN, PNP [3 5] PNNP, [13 18] (PNNP ), PNNP2Ru [6 8] Ξ E2mail : xmu edu cn Received March 29, 2004 ; revised June 4, 2004 ; accepted July 13, 2004 (No ) (No 2002F016) (No 3502Z )

2 1746 Vol 62, 2004 PNNP/ Ru 3 (CO) 12 [19 22],, 2 1, 1 ( S, S) 21, ( S,, S) 22 ( R, R)23 KOH PE Spectroy 2000 SP3420 ( : CP2 cyclodextrin M219, 50 m) Fe 3 ( CO) 12 [ Et 3 NH] + [ HFe 3 (CO) 11 ] - [23] 1 2, Na 2 SO 4, ( S, S) 2 ( R, R)21,22,, NaBH 4 [19,20], 1 3 Schlenk 1 Figure 1 Chiral diaminodiphosphine ligand,, 20 min, KOH/, i2proh, 10 min 45,, 1 a 1 Table 1 Asymmetric transfer hydrogenation of propiophenone with various catalyst systems a Entry Fe complex Ligand S C KOH Time/ h Yield b / % ee c / % Config d 1 CpFe (CO) 2 I ( S, S) R 2 CpFe (CO) 2 I ( R, R) S 3 Fe 2 (CO) 9 ( S, S) Fe 2 (CO) 9 ( R, R) [ CpFe (CO) 2 ] 2 ( S, S) R 6 [ CpFe (CO) 2 ] 2 ( R, R) S

3 No 18 : 1747 Entry Fe complex Ligand S C KOH Time/ h Yield b / % ee c / % Config d 7 Fe 3 (CO) 12 ( S, S) R 8 Fe 3 (CO) 12 ( R, R) S 9 [ Et 3 NH] + [ HFe 3 (CO) 11 ] - ( R, R) S 10 [ Et 3 NH] + [ HFe 3 (CO) 11 ] - ( S, S) R a Reaction was carried out by using 0 1 mol/ L solution of substrate in i2proh at 45, S C = [ Ketone ] [ Fe ] Chromack CP2cyclodextrin M219 column (50 m) b GLC analysis c Capillary GLC analysis using a chiral d Determined by comparison of the retention times of the enantiomers on the GLC traces with literature values 1 90 % 72 % ee ( 1, Entry 9), CpFe(CO) 2 I ( 1, Entries 1, 2) Fe 2 (CO) 9 ( 1, Entries 3, 4 ) 2 2 [ Et 3 NH] + [ HFe 3 ( CO) 11 ] - Fe 2 (CO) 9, ee, [ Et 3 NH] + 2 ( 1, Entries 5, 6) [ HFe 3 (CO) 11 ] - Fe 3 (CO) 12, 90 % ee ( 1, Entries 7, 8) [ Et 3 NH] + [ HFe 3 (CO) 11 ] - / C 6 P 2 (NH) 2 [ Et 3 NH] + [ HFe 3 ( CO) 11 ] [ Et 3 NH] + [ HFe 3 (CO) 11 ] - a Table 2 Asymmetric transfer hydrogenation of various aryl ketones catalyzed by chiral aminophosphine [ Et 3 NH] + [ HFe 3 (CO) 11 ] - systems a Entry Substrate Ligand Temp / Time/ h Yield b / % ee c / % Config d 1 ( S, S) R 2 ( R, R) S 3 ( R, R) S 4 ( S, S) S 5 ( S, S) R 6 ( S, S) R 7 ( S, S) R 8 ( S, S) R

4 1748 Vol 62, 2004 Entry Substrate Ligand Temp / Time/ h Yield b / % ee c / % Config d 9 ( S, S) S 10 ( S, S) S a Reaction was carried out by using 011 mol/ L solution of substrate in i2proh; S C KOH = b GLC analysis CP2cyclodextrin M219 column (50 m) c Capillary GLC analysis using a chiral Chromack d Determined by comparison of the retention times of the enantiomers on the GLC traces with literature values 2 ( 2, Entries 1 4) 93 % ee 82 7 h, 19 % ( 2, Entry 4), S, ee ( 2, Entry 5), ( 2, Entry 7) ; 2, ee 49 % ( 2, Entry 8) Figure 2 The effect of temperature on asymmetric transfer hydrogenation of isopropyl phenyl ketone ee ( 2, Entries 6 8), ee 98 %( 2, Entry 9) ee ( 2, Entry 10) Fe 3 (CO) 12 / ( R, R)23 60, 2, ee, 90 %, Fe 3 (CO) 12, , 7 h, 83 %, ee Figure 3 The effect of reaction time on asymmetric transfer 79 % 73 % Catalyst : [ Et 3 NH] [ HFe 3 (CO) 11 ]/ ( S, S)22 ; substrate : acetophenone ; S C KOH = ; temperature : 82 4 KOH Catalyst : Fe 3 (CO) 12 / ( R, R)23 ; substrate : isopropyl phenyl ketone ; substrate catalyst KOH = (S C KOH molar ratio) ; reaction time : 7 h 3 hydrogenation of acetophenone

5 No 18 : Figure 4 The effect of addition of KOH on asymmetric transfer hydrogenation of acetophenone Catalyst : [ Et 3 NH ] [ HFe 3 ( CO) 11 ]/ ( S, S )22 ; substrate : acetophenone ; temperature : 82 ; S C = ; reaction time : 7 h KOH 0101 mmol 0102 mmol, 18 % 83 % 0103 mmol, 7 h,, ee, 80 % 40 %, 0102 mmol, 83 % 73 % ee Fe 3 (CO) 12 Figure 5 IR spectra (in CaF 2 ) derived from (a) Fe 3 (CO) 12 in i2 PrOH, (b) after the addition of KOH/ i2proh to Fe 3 (CO) 12 in i2 PrOH for 10 min, (c) after the addition of ( S, S)21 to Fe 3 (CO) 12 / : i2prok in i2proh for 45 min, ( d ) after the addition of acetophenone to Fe 3 (CO) 12 / i2prok/ ( S, S)21 in i2proh for 2 h, and (e) after the addition of acetophenone to Fe 3 (CO) 12 / i2prok/ ( S, S)21 in i2proh for 4 h, References ( S, S)21/ Fe 3 (CO) 12, 5 1 Noyori, R Asymmetric 5, 2049 Catalysis in Organic Synthesis, John 1901 cm - 1 ( 5, a) Wiley, New York, 1994, pp Takaya, H ; Noyori, R Catalytic Asymmetric Synthesis, Ed : KOH, Fe 3 (CO) 12, Ojima, I, VCH, Berlin, 1993, pp ( 5, b) ( S, S)21, 3 Noyori, R ; Hashiguchi, S Acc Chem Res 1997, 30, 97, ( 5, c, d) 4 Palmer, M J ; Wills, M Tetrahedron : Asymmetry 1999, 10, 4 h, 2075 (m), 1969 ( s), 1941 (m) 1902 ( s) 2045 cm - 1 ( 5, e) 5 Blaser, H U ; Malan, C ; Pugin, B ; Spindler, F ; Steiner, F ; Steiner, H ; Studer, M Adv 103 Synth Catal 2003, 345, 6 Burk, M Acc Chem Res 2000, 33, Blaser, H U ; Brieden, W ; Pugin, B ; Spindler, F ; Studer, A ; Togni, A Top Catal 2002, 19, 3

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