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 触媒機能 構造とその触媒機能

（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

H2 M N M H N H A B A B H H N H S O R O N H S O O R

Tethered arene Ru(II) complexes Organometallics 2008.

Ts = CH3C6H4SO2, Tf = CF3SO2

Rh, Ir COMPLEXES WITH TETHERED Cp* LIGAND

A i h d i f i i Asymmetric hydrogenation of imines

N C6H5 pre-catalyst AgSbF6 (4 equiv.) MS 4A HN C6H5 H2 30 atm 2-propanol, 30 °C, 17 h S/C = 100 up to >99% yield S/C = 100 T T T pre-catalyst up to >99% yield up to 72% ee Ir N N Cl Ru N N Cl Ts Ts Rh N N Cl Ts

Organometallics 2009.

H H H H 68% yield 99% yied H H 99% yied

Triflylamide terminal

PREPARATION OF Rh, Ir DIMER WITH SULFONYLAMIDE SIDE CHAIN

Tf2O, N(C2H5)3 CH Cl 78 °C NH O NTf O Li (2 equiv.) HO NHTf

n 1

THF 78 °C rt CH2Cl2, 78 C

n 1 n 1

THF, 78 C rt n = 2, 39% yield n = 3, 38% yield n = 4 59% yield MCl • 3H O (0 33 equiv ) Cl Cl n = 4, 59% yield

ORTEP drawing of Rh dimer (n = 4)

n 1 n 1

MCl3• 3H2O (0.33 equiv.) CH3OH, reflux M Cl Cl M Cl TfHN NHTf

Rh

ORTEP drawing of Rh dimer (n = 4)

M = Rh n = 2, 55% yield n = 3, 83% yield n = 4 92% yield M = Ir n = 2, 19% yield n = 3, 72% yield n = 4 41% yield

Rh NHTf

n 4, 92% yield n 4, 41% yield

Rh NHTf

Pbca (#61) R1 = 0.0335 wR2 = 0.0714

TETHERED ACETONITRILE COMPLEXES

Reaction with Ag2CO3 C(1) ORTEP drawing of Ir complex (n = 4) Ir Selected bond lengths (Å) and angles (˚) n = 2 n = 3 n = 4 N(1) N(2) Cl Ir―N(1) Ir―C(1) C(1) Ir N(1) 2.134(9) 2.102(11) 81 4(4) 2.118(3) 2.130(3) 90 56(13) 2.154(4) 2.155(5) 97 95(18) C(1)―Ir―N(1) 81.4(4) 90.56(13) 97.95(18) P21/c(#14) R1 = 0.0287 wR2 = 0.0640

REACTION WITH MsDPEN LIGAND

NMR study for NH2 ligand

• Adv. Synth. Catal. 2004.

Ms = CH3SO2

ORTEP DRAWINGS FOR TETHERED MsDPEN COMPLEXES

Ir C1 Ir C1 N1 N2 N3 S1 S1 N1 N3 O1 P2 (#4) O1 S1 N2 P2 (#4) P21 (#4) R1 = 0.0457 wR2 = 0.1089 P21 (#4) R1 = 0.0287 wR2 = 0.0726 Selected bond lengths (Å) and angles (˚) Ir―N(1) Ir―N(2) 2.175(7) 2.147(7) Selected bond lengths (Å) and angles (˚) Ir―N(1) Ir―N(2) 2.140(4) 2.116(4) ( ) Ir―N(3) N(2)―O(1) C(1) ―N(1) ―S(1) ( ) 2.132(6) 2.796(6) 115.0(6) ( ) Ir―N(3) N(2)―O(1) C(1) ―N(1) ―S(1) ( ) 2.129(4) 2.756(4) 120.4(3) ( ) ( ) ( ) C(1) ―N(1) ―Ir S(1) ―N(1) ―Ir ( ) 113.5(6) 131.2(4) Total 359.7 ˚ ( ) ( ) ( ) C(1) ―N(1) ―Ir S(1) ―N(1) ―Ir ( ) 106.8(4) 131.5(3) Total 357.7 ˚

REVERSIBILITY OF TETHERED/UNTETHERED Ir COMPLEXES

Reaction with acid/base

ASYMMETRIC HYDROGENATION

Tether length effect

O OH (R,R)-catalyst (R) CH3OH, 30 C, 24 h S/C = 100, [ketone] = 0.25 M H2 30 atm (R) n yield, %a ee, %b M 2 40 20 (R,R)-catalyst Rh 3 58 29 S/C 200 yield, %a ee, %b 80 94 2 37 94 M N NH2 MsN

n 1

Ir 4 94 93 500 92 59 2 3 53 37 94 NH2Tf C6H5 C6H5 86 Ir 200 80 94 S/C yield, %a ee, %b 4 90 92

a1H NMR analysis, bHPLC analysis

500 68 91

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