4G03 Ru, Rh, Ir - PowerPoint PPT Presentation

4G03 機能性アミノテザーを有する Ru, Rh, Ir 錯体の 構造とそ 構造とその触媒機能 触媒機能 （東京工大） 伊藤正人・遠藤慶徳・手島典子・碇屋隆雄

BACKGROUND Amido-amine interconversion system Application to tethered complexes Organometallics 2008, Chem. Lett. 2009.

TETHERED TRIFLYLAMIDE COMPLEXES FOR HYDROGENATION H 2 M M N N H H H H N N O O S S A B A B O O R R H H Tethered arene Ru(II) complexes Organometallics 2008. Ts = CH 3 C 6 H 4 SO 2 , Tf = CF 3 SO 2

Rh, Ir COMPLEXES WITH TETHERED Cp* LIGAND Asymmetric hydrogenation of imines A i h d i f i i pre-catalyst AgSbF 6 (4 equiv.) N C 6 H 5 HN C 6 H 5 MS 4A H 2 2-propanol, 30 °C, 17 h 30 atm S/C = 100 S/C = 100 up to >99% yield up to >99% yield up to 72% ee pre-catalyst Ts T T Ts T Ts N N N Ru Rh Ir N N Cl N Cl Cl H H H H H H 68% yield 99% yied 99% yied Organometallics 2009.

PREPARATION OF Rh, Ir DIMER WITH SULFONYLAMIDE SIDE CHAIN Triflylamide terminal NHTf O O HO n 1 (2 equiv.) Tf 2 O, N(C 2 H 5 ) 3 Li NTf NH CH Cl CH 2 Cl 2 , 78 °C 78 C THF THF, 78 °C 78 C rt rt n 1 n 1 n = 2, 39% yield n = 3, 38% yield n = 4 59% yield n = 4, 59% yield Cl Cl Cl MCl 3 • 3H 2 O (0.33 equiv.) MCl • 3H O (0 33 equiv ) n 1 NHTf M M TfHN CH 3 OH, reflux n 1 Cl Cl ORTEP drawing of Rh dimer ( n = 4) ORTEP drawing of Rh dimer ( n = 4) M = Rh M = Ir n = 2, 55% yield n = 2, 19% yield n = 3, 83% yield n = 3, 72% yield n = 4 92% yield 4, 92% yield n = 4 41% yield 4, 41% yield n n Rh Rh NHTf NHTf Pbca (#61) Rh R 1 = 0.0335 wR 2 = 0.0714

TETHERED ACETONITRILE COMPLEXES Reaction with Ag 2 CO 3 ORTEP drawing of Ir complex ( n = 4) C(1) Ir N(1) N(2) Selected bond lengths (Å) and angles ( ˚ ) Cl n = 2 n = 3 n = 4 Ir ― N(1) 2.134(9) 2.118(3) 2.154(4) Ir ― C(1) 2.102(11) 2.130(3) 2.155(5) C(1) C(1) ― Ir ― N(1) Ir N(1) 81 4(4) 81.4(4) 90 56(13) 90.56(13) 97 95(18) 97.95(18) P 2 1 / c (#14) R 1 = 0.0287 wR 2 = 0.0640

REACTION WITH MsDPEN LIGAND NMR study for NH 2 ligand Adv. Synth. Catal. 2004. Ms = CH 3 SO 2

ORTEP DRAWINGS FOR TETHERED MsDPEN COMPLEXES Ir C1 C1 Ir N1 N1 N3 N2 N3 S1 S1 S1 N2 O1 O1 P 2 (#4) P 2 1 (#4) P 2 1 (#4) P 2 (#4) R 1 = 0.0287 R 1 = 0.0457 wR 2 = 0.0726 wR 2 = 0.1089 Selected bond lengths (Å) and angles ( ˚ ) Selected bond lengths (Å) and angles ( ˚ ) Ir ― N(1) 2.140(4) Ir ― N(1) 2.175(7) Ir ― N(2) ( ) Ir ― N(2) ( ) 2.116(4) ( ) 2.147(7) ( ) Ir ― N(3) Ir ― N(3) 2.129(4) 2.132(6) N(2) ― O(1) N(2) ― O(1) 2.756(4) 2.796(6) C(1) ― N(1) ― S(1) ( ) ( ) ( ) 120.4(3) ( ) C(1) ― N(1) ― S(1) ( ) ( ) ( ) 115.0(6) ( ) C(1) ― N(1) ― Ir C(1) ― N(1) ― Ir 106.8(4) 113.5(6) S(1) ― N(1) ― Ir S(1) ― N(1) ― Ir 131.5(3) 131.2(4) Total 357.7 ˚ Total 359.7 ˚

REVERSIBILITY OF TETHERED/UNTETHERED Ir COMPLEXES Reaction with acid/base

ASYMMETRIC HYDROGENATION Tether length effect O OH ( R,R )-catalyst ( R ) ( R ) H 2 CH 3 OH, 30 C, 24 h 30 atm S/C = 100, [ketone] = 0.25 M yield, % a ee, % b n M Rh 2 40 20 yield, % a S/C ee, % b ( R,R )-catalyst 3 58 29 200 80 94 4 94 93 500 59 92 M n 1 MsN N NH 2 NH 2 Tf Ir Ir 2 2 37 37 94 94 yield, % a S/C ee, % b C 6 H 5 C 6 H 5 3 53 86 200 80 94 4 90 92 500 68 91 a 1 H NMR analysis, b HPLC analysis

ASYMMETRIC HYDROGENATION Solvent effect

POSSIBLE MECHANISM OF ASYMMETRIC HYDROGENATION

SUMMARY Synthesis of tethered sulfonylamide Cp’Rh, Ir complexes and their derivatives Asymmetric hydrogenation of ketones Asymmetric hydrogenation of ketones