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Mar 04, 2024 •408 likes •534 views

Cp*Ru(PN) HYDROGENATION OF POLAR BONDS WITH BIFUNCTIONAL Cp*Ru(II) CATALYSTS heterolytic

  1. キラ ル Cp*Ru(PN) 触媒による 対称環状イ ミ ド 類の不斉水素化 （ 東工大院理工） 伊藤正人○小林知佳・ 碇屋隆雄

  2. HYDROGENATION OF POLAR BONDS WITH BIFUNCTIONAL Cp*Ru(II) CATALYSTS heterolytic cleavage of H 2 H 2 , ROH H Ru L H N O H H R L = N(CH 3 ) 2 ketones ROH Ru Ru Cl L L NH N H base H L = PPh 2 epoxides, imides Ru L H N H A B H H H 18e amine-Ru hydride A B M. Ito, T. Ikariya, Chem. Commun ., 2007 , 5134-5142.

  3. ENANTIOSELECTIVE HYDROGENATION OF GLUTARIMIDE O O O O Cp*RuCl(PN) KO t -C 4 H 9 O O + H 2 Ar HN * Ar N 2-propanol R 30 atm OH O >99% yield Ar = p -FC 6 H 4 >99% ee O 1) CBr 4 , PPh 3 Ar NH * 2) NaH R 3) CAN Ru Ph 2 P RO Cl NH Ar NH 2 Cl Cp*RuCl(PN) ( –)-paroxetine HCl M. Ito, A. Sakaguchi, C. Kobayashi, T. Ikariya, J. Am. Chem. Soc. 2007, 129 , 290.

  4. ASYMMETRIC HYDROGENATION OF meso -SUCCINIMIDES O O O O Cp*RuCl(PN) KO t -C 4 H 9 O + H 2 O HN N 2-propanol 30 atm OH O Reaction conditions : S/C = 10, [imide] = 0.2 M in 2-propanol, 24 h, 80 ° C. O O O NR NR NR Ru Ph 2 P Cl NH O O O Cp*RuCl(PN) 62% ee 63 55

  5. THIS WORK O O R' R' Ru Cp*Ru Ph 2 P Cl N R + H 2 NHR NH R' R' O OH Cp*RuCl(PN) R = 3,4-methylenedioxyphenyl Preparation of new PN ligands Ph Ph N PPh 2 N N PPh 2 PPh 2 H H H

  6. SYNTHESIS OF NEW CHIRAL PN LIGANDS Ph Ph S O S S O N N OH O N OH OTs S N H HHCl PPh 2 Boc H K. Tomioka, J. Org. Chem. 2003 , 68 , 9723. LiAlH 4 Ph Ru [Ru] Ph Ph 2 P Cl Ru NH Ph 2 P Cl N PPh 2 [Ru] H NH N PPh 2 H [Ru] = Cp*RuCl(isoprene) Ph Ph Ts = p -toluenesulfonyl Boc = t -butoxycarbonyl

  7. SYNTHESIS OF LIGAND DERIVED FROM PIPECOLIC ACID HPPh 2 BH 3 •THF NaH TfOH N N THF toluene N CO 2 H N H Boc Boc reflux O PPh 2 OH O 24 h 59% yield 77% yield (2 steps) The Annual Meeting of Chemical Society of Japan, 2001, 1H317 Cp*RuCl(isoprene) Ru Ph 2 P Cl CH 2 Cl 2 NH 76% yield light yellow powder 1 H NMR (CD 2 Cl 2 ) δ 1.34 (d, J = 1.7 Hz, 15H, Cp*) P 2 1 (#4) 31 P NMR (CD 2 Cl 2 ) R 1 = 0.0531 δ 55.0 ppm wR 2 = 0.1353

  8. HYDROGENATION OF meso -SUCCINIMIDES BY NEW Cp*Ru(PN) O O O O Cp*Ru(PN) KO t- C 4 H 9 O O + H 2 N HN 2-propanol 30 atm O OH Reaction conditions: S/C = 10, [imide] = 0.1 M in 2-propanol, 24 h, 80 ° C. Cp*Ru(PN) Ru Ru Ru Ru Ph 2 P Ph 2 P Ph 2 P Ph 2 P Cl Cl Cl Cl NH NH NH NH Ph Ph >99% conv >99% conv 19% conv >99% conv 52% ee 68% ee 50% ee 76% ee

  9. HYDROGENATION OF SUCCINIMIDES WITH Cp*Ru WITH PIPERIDINE RING O O O O O NR NR NR NR NR O O O O O Ru Ph 2 P Cl 70% ee 53 91 81 92 NH 62 63 52 55 Ru Ph 2 P Cl NH Reaction conditions: S/C = 10, [imide] = 0.1 M in 2-propanol, 24 h, 80 ° C. R = 3,4-methylenedioxyphenyl

  10. APPLICATION : physiologically active compounds pyrethroid CN OPh OPh CO 2 CO 2 Cl Br Cl Br decamethrin permethrin SNRI Ph CH 2 NH 2 Et 2 NOC milnacipran

  11. SUMMARY Asymmetric hydrogenation of succinimides O O O O Cp*RuCl(PN*) R R KO t -C 4 H 9 O O Ru + H 2 N HN 2-propanol Ph 2 P Cl NH R R 30 atm O OH >99% yield Cp*RuCl(PN) S/C = 10, 24 h, [imide] = 0.1 M in 2-propanol, 80 ° C CONHAr CONHAr CONHAr CONHAr CONHAr HOCH 2 CONHAr CH 2 OH CH 2 OH CH 2 OH CH 2 OH CH 2 OH 76% ee 70% ee 53% ee 91% ee 81% ee 92% ee

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