Cp*Ru(PN) - - PowerPoint PPT Presentation

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Cp*Ru(PN) - - PowerPoint PPT Presentation

Mar 04, 2024 408 likes •538 views

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

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SLIDE 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

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SLIDE 2

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

18e amine-Ru hydride H2, ROH A B A B H H Ru H L N H H Ru L N H H H H O R Ru Cl L N H H base L = N(CH3)2 ketones L = PPh2 epoxides, imides ROH Ru L NH heterolytic cleavage of H2

  • M. Ito, T. Ikariya, Chem. Commun., 2007, 5134-5142.
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SLIDE 3

N Ar O O

*

HN Ar O OH Cp*RuCl(PN) KOt-C4H9 2-propanol + H2 30 atm 1) CBr4, PPh3 2) NaH 3) CAN

*

NH Ar O

R R

( –)-paroxetine HCl Ar = p-FC6H4

ENANTIOSELECTIVE HYDROGENATION OF GLUTARIMIDE

NH2Cl Ar RO Ru Cl Ph2P NH Cp*RuCl(PN) O O O O >99% yield >99% ee

  • M. Ito, A. Sakaguchi, C. Kobayashi, T. Ikariya, J. Am. Chem. Soc. 2007, 129, 290.
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SLIDE 4

NR O O Reaction conditions : S/C = 10, [imide] = 0.2 M in 2-propanol, 24 h, 80 °C.

ASYMMETRIC HYDROGENATION OF meso-SUCCINIMIDES

Ru Cl Ph2P NH NR O O NR O O Cp*RuCl(PN) N O O HN O OH + H2 30 atm Cp*RuCl(PN) KOt-C4H9 2-propanol O O O O 62% ee 63 55

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SLIDE 5

N H PPh2 Ph Ph N H PPh2 N PPh2 Preparation of new PN ligands Ru Cl Ph2P NH H

THIS WORK

N R' R' O O R NHR R' R' O OH + H2 Cp*RuCl(PN) Cp*Ru R = 3,4-methylenedioxyphenyl

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SLIDE 6

N H O OH N H Ph Ph PPh2 N H O Ph Ph PPh2 S

SYNTHESIS OF NEW CHIRAL PN LIGANDS

N HHCl OH O N Boc OTs N H PPh2 Ru Cl Ph2P NH Ru Cl Ph2P NH Ph Ph Ts = p-toluenesulfonyl Boc = t-butoxycarbonyl S S S [Ru] [Ru] = Cp*RuCl(isoprene) [Ru]

  • K. Tomioka, J. Org. Chem. 2003,

68, 9723. LiAlH4

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SLIDE 7

N Boc CO2H N O O N H PPh2 HPPh2 TfOH toluene reflux 24 h

SYNTHESIS OF LIGAND DERIVED FROM PIPECOLIC ACID

Cp*RuCl(isoprene) CH2Cl2 77% yield 76% yield

1H NMR (CD2Cl2)

δ 1.34 (d, J = 1.7 Hz, 15H, Cp*)

31P NMR (CD2Cl2)

δ 55.0 ppm BH3•THF NaH 59% yield (2 steps) light yellow powder P21 (#4) R1 = 0.0531 wR2 = 0.1353 THF N Boc OH Ru Cl Ph2P NH The Annual Meeting of Chemical Society

  • f Japan, 2001, 1H317
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SLIDE 8

Ru

HYDROGENATION OF meso-SUCCINIMIDES BY NEW Cp*Ru(PN)

N O O >99% conv 52% ee Cp*Ru(PN) O O Cp*Ru(PN) KOt-C4H9 2-propanol Reaction conditions: S/C = 10, [imide] = 0.1 M in 2-propanol, 24 h, 80 °C. HN O OH O O >99% conv 68% ee >99% conv 76% ee 50% ee 19% conv Ru Cl Ph2P NH Ru Cl Ph2P NH Ru Cl Ph2P NH Ph Ph Cl Ph2P NH + H2 30 atm

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SLIDE 9

NR O O NR O O NR O O NR O O NR O O 91 92 70% ee 53 81 Reaction conditions: S/C = 10, [imide] = 0.1 M in 2-propanol, 24 h, 80 °C. R = 3,4-methylenedioxyphenyl

HYDROGENATION OF SUCCINIMIDES WITH Cp*Ru WITH PIPERIDINE RING

Ru Cl Ph2P NH 62 63 52 55 Ru Cl Ph2P NH

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SLIDE 10

decamethrin

APPLICATION : physiologically active compounds

permethrin CH2NH2 Et2NOC Ph milnacipran

SNRI

pyrethroid CO2 Br Br CN OPh CO2 Cl Cl OPh

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SLIDE 11

S/C = 10, 24 h, [imide] = 0.1 M in 2-propanol, 80 °C

SUMMARY

Cp*RuCl(PN*) KOt-C4H9 2-propanol + H2 Cp*RuCl(PN) >99% yield 30 atm Asymmetric hydrogenation of succinimides N R R O O O O HN R R O OH O O CONHAr CH2OH CONHAr CH2OH HOCH2 CONHAr 70% ee 76% ee 53% ee Ru Cl Ph2P NH CONHAr CH2OH CONHAr CH2OH CONHAr CH2OH 91% ee 81% ee 92% ee