: 5 - Rh - PowerPoint PPT Presentation

1L2-51 テザー型 ( η １ : η 5 - アミ ノ アルキルシク ロペンタ ジエニル） Rh Ｃ ｌ 錯体の合成と その触媒機能 ２ （ 東工大院理工） 伊藤正人○手島典子・ 碇屋隆雄

CATALYTIC LEUCKART － WALLACH TYPE REDUCTIVE AMINATION OF KETONES O NH 2 OH Rh cat + HCO 2 NH 4 Cl + C 6 H 5 C 6 H 5 C 6 H 5 CH 3 OH Rh H 5 equiv H 70 °C, 2 h Cl 2 substrate/[Rh] = 100 98:2 Cp*Rh dimer 98% conv Possible mechanism NH 2 OCH O HCO 2 NH 4 CO 2 O Rh C 6 H 5 C 6 H 5 Cl NH 3 + H 2 O H byproduct NH 2 OH Rh Cl + NH 3 C 6 H 5 C 6 H 5 O HCO 2 NH 4 H H Rh H O – NH 4 Cl Cl NH 3 Cl Kitamura, M. Lee, D. Hayashi, S. Tanaka, S. Yoshimura, M. J. Org. Chem. 2002, 67 , 8685.

DESIGN OF Rh TETHERED COMPLEX +NH 3 Rh Rh Rh NH 3 Cl Cl NH 3 –NH 3 H H possible active catalyst This work Rh Rh Cl Cl N N R R' R R' H H R, R' = H, CH 3

SYNTHESIS OF C 2 TETHERED COMPLEXES NRR' NRR' NRR' •HCl 1) HCO 2 C 2 H 5 HCl in (C 2 H 5 ) 2 O CH 3 OH 2) LiAlH 4 50 °C, 2 h R, R' = H, CH 3 + two isomers Hessen , B . Organometallics, 2000, 19 , 4084. NRR'•HCl (CH 3 ) 3 COK (1 equiv/Rh) RhCl 3 •3H 2 O Cl Rh Cl CH 2 Cl 2 , rt, 9 h CH 3 OH N Rh Cl Rh reflux, 72 h Cl R R' Cl Cl orange powder R, R' = H 36% yield R = H, R' = CH 3 27% yield HCl• R'RN R, R' = CH 3 23% yield orange powder R, R' = H, CH 3 R = H, R' = CH 3 1 H NMR ( δ , CDCl 3 ) 13 C NMR ( δ , CDCl 3 ) 106.2 (d, 2 J RhC = 8.8 Hz, C 5 (CH 3 ) 4 ) 3.89 (m, 2H, C H 2 NHCH 3 ) 3.58 (br, 1H, NH) 99.3, 95.9, 87.6, 84.5 ( C 5 (CH 3 ) 4 ) 2.54 (d, 3H, 3 J = 6.1 Hz, NHC H 3 ) 66.6, 39.3, 23.5, 9.3, 8.7 2.36 –2.45 (m, 2H, C H 2 CH 2 NHCH 3 ) 1.89, 1.86, 1.71, 1.67 (s, 3H each, C H 3 )

SYNTHESIS OF C 3 TETHERED COMPLEX NHBoc NBoc 1) 2) H 2 O OH Br Li O HCl in (C 2 H 5 ) 2 O (1 equiv) Li CH 3 OH (C 2 H 5 ) 2 O THF 0 °C, 4 h － 78 °C → rt, 3 h 50 °C, 4 h Boc = CO 2 C(CH 3 ) 3 NH 3 Cl (CH 3 ) 3 COK (1 equiv) RhCl 3 •3H 2 O Rh Cl N CH 2 Cl 2 , rt, 9 h CH 3 OH H 2 Cl reflux, 12 h orange powder + two isomers 37% yield 1 H NMR ( δ , CDCl 3 ) 13 C NMR ( δ , CD 2 Cl 2 ) 98.7 (d, 2 J RhC = 7.6 Hz, C 5 (CH 3 ) 4 ) 3.30 (br, 2H, (CH 2 ) 2 C H 2 NH 2 ) 96.4 (d, 2 J RhC = 8.4 Hz, C 5 (CH 3 ) 4 ) 2.68 (br, 2H, NH 2 ) 86.4 (d, 2 J RhC = 9.5 Hz, C 5 (CH 3 ) 4 ) 2.14 –2.10 (m, 2H, C H 2 (CH 2 ) 2 NH 2 ) 39.5, 30.3, 18.9, 9.1, 8.5 2.03 (br, 2H, CH 2 C H 2 CH 2 NH 2 ) 1.80, 1.66 (s, 6H each, C 5 C H 3 )

MOLECULAR STRUCTURES OF C 2 AND C 3 TETHERED DERIVATIVES n n NHTf (CH 3 ) 3 COK (2 equiv) Rh + TfN N Rh THF, reflux, 9 h Cl H 2 N NHTf NTf H 2 Cl Tf = CF 3 SO 2 n = 0, 1 n = 0, 1 orange crystals P 2 1 / n (#14) P 2 1 / a (#14) R 1 = 0.033 R 1 = 0.034 wR 2 = 0.120 wR 2 = 0.130

SYNTHESIS OF CATIONIC TETHERED COMPLEXES SbF 6 n n 1) AgSbF 6 2) P(C 6 H 5 ) 3 Rh Rh THF, rt Cl N (C 6 H 5 ) 3 P N H 2 H 2 Cl Cl n = 0, 1 orange powders n = 0 33% yield n = 1 45% yield n = 0 n = 1 1 H NMR ( δ , CD 2 Cl 2 ) 1 H NMR ( δ , CD 2 Cl 2 ) 7.43 –7.58 (m, 15H, C 6 H 5 ) 7.46 –7.58 (m, 15H, C 6 H 5 ) 3.94 (m, 1H) 2.73 (br, 2H) 3.77 (m, 2H) 2.61 (br, 1H) 2.67 (m, 2H) 2.05 –2.35 (m, 5H) 1.83 (d, 3H, 4 J HP = 6.8 Hz, CH 3 ) 2.20 –2.28 (m, 1H) 2.13 (d, 3H, 4 J HP = 7.6 Hz, CH 3 ) 1.74 (s, 3H, CH 3 ) 1.69 (s, 3H, CH 3 ) 1.08 (s, 3H, CH 3 ) 0.97 (d, 3H, 4 J HP = 5.9 Hz, CH 3 ) 1.21 (s, 3H, CH 3 ) 0.97 (d, 3H, 4 J HP = 5.4 Hz, CH 3 ) 31 P NMR ( δ , CD 2 Cl 2 ) 34.8 (d, 1 J PRh = 141.6 Hz) 31 P NMR ( δ , CD 2 Cl 2 ) 33.1 (d, 1 J PRh = 141.0 Hz)

CATALYTIC REACTION Reductive amination of benzaldehyde H Rh cat O HN C 6 H 5 N C 6 H 5 OH + • HCO 2 H + CH 3 OH C 6 H 5 C 6 H 5 70 °C, 2 h 0.1 M in CH 3 OH 1 equiv substrate/[Rh] = 100 amine:alcohol cat. TON dimer 54:46 58 R, R' = H 96:4 68 C 2 Cl Rh Rh Rh N Cl C 2 R = H, R' = CH 3 83:17 68 N Cl Cl R R' 2 H 2 Cl Cl R, R' = CH 3 88:12 70 C 2 dimer R, R' = H, CH 3 C 2 C 3 65:35 63 C 3 determined by NMR

SUMMARY Synthesis of Rh tethered complexes SbF 6 n n Rh Rh Rh Rh TfN Cl Ph 3 P Cl N N N N H 2 H 2 CH 3 H 2 NTf Cl Cl Cl R R = H, CH 3 n = 0, 1 Reductive amination R 1 R 1 R 1 Rh cat R 3 R 3 ・ HCO 2 H + + HN C 6 H 5 N C 6 H 5 OH C 6 H 5 O CH 3 OH 70 °C, 2 h R 2 R 2 1 equiv 0.1 M in CH 3 OH substrate/[Rh] = 100 amine : alcohol = up to 96 : 4 R 1 = H, R 2 , R 3 = CH 2 C 6 H 5

STRUCTURE OF TETHER RINGS C 0 C 0 θ θ Rh Rh N N C 2 C 3 θ (°) Rh – N(Å) Rh – C 0 (Å) C 2 2.094(5) 93.8(2) 2.139(4) 2.114(4) C 3 2.147(4) 81.7(2)

Sbstrate scope R 1 R 1 R 1 Rh cat R 3 R 3 ・ HCO 2 H + + HN C 6 H 5 N C 6 H 5 OH C 6 H 5 O CH 3 OH 70 °C, 2 h R 2 R 2 1 equiv 0.1 M in CH 3 OH substrate/[Rh] = 100 amine:alcohol TON R 1 R 2 R 3 CH 3 43 H H 93:7 H -(CH 2 ) 4 - 98:2 99 -(CH 2 ) 4 - CH 3 90:10 14