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( - a r e n e ) R u 6

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SLIDE 1

アミ ノ チオール配位子をも つ ( η6

  • a

r e n e ) R u 錯体の合成と その触媒機能

東京工業大学大学院理工学研究科 伊藤正人・ 柴田祐二・ 碇屋隆雄

２ ０ ０ ７ 年１ ０ 月２ ８ 日 第５ ４ 回有機金属化学討論会A 2 6

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SLIDE 2

Ru Cl Me2 N N H2 Ru Cl Ph2 P N H2 R1 R2 OH R1 R2 O R1 R2 O R1 R2 OH Ru L NH H Ru L N H H

Cp*Ru(AMINE) CATALYSTS FOR RACEMIZATION OF CHIRAL sec-ALCOHOLs

inactive highly active up to 479 TOF/h Tetrahedron Lett. 2003, 44, 7521 Conditions: Ru + KOt-Bu (1:1), [alcohol] = 0.1–1.0 M in toluene, 30 ºC

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SLIDE 3

>1000 TOF/h at 30 °C >2500 TOF/h at 30 °C

  • Org. Lett. 2007, 9, 1821

OXIDATIVE TRANSFORMATION OF ALCOHOLs WITH Cp*Ru(PN) CATALYSTS

– H2 + H2 O OH CH2OH OH OH O O O – H2 – H2 R1 R4 R3 R2 OH R1 R4 R3 R2 O R1 R4 R3 R2 O intramolecular hydrogen transfer of allylic alcohols: concise synthesis of muscone intrermolecular hydrogen transfer from diol to acetone: synthesis of γ-lactones

  • J. Am. Chem. Soc. 2005, 127, 6172

O O O n-C12H25 OH muscone muricatacin

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SLIDE 4

ISOELECTRONIC Ru–AMINE COMPLEXES

Ru Cl O N H2 Ru Cl Me2 N N H2 Ru Cl Ph2 P N H2 Ru Cl Ts N N H2 Ru Cl S N H2 Ru Cl Cl N H2

n( )

Ru Cl L N H2 Ru Cl X N H2

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SLIDE 5

(η6-arene)Ru(AMINE) CATALYSTS FOR CHEMOENZYMATIC ASYMMETRIC SYNTHESIS Ru Cl Ts N N H2

  • R. A. Sheldon Tetrahedon: Asymmetry, 2002, 13, 879.
  • A. R. A. Palmans J. Am. Chem. Soc, 2005, 127, 9964.

O O O O OR n Novozym 435 Ru + base n OH Ru + KOH (1 mol%) 70 °C, 48 h OH >99% ee 0% ee Ru Cl H N N H2 O Ph ROH

  • A. Heise, Angew. Chem. Int. Ed. 2006, 45, 2130.

92% ee (n = 5) 0% ee

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SLIDE 6

KOt-Bu toluene, 30 °C OH OH [(hmb)RuCl2]2 X –NH2 SH NH2 X –NH2 ligand ee, % 7 14 76 >99% ee 24 h alcohol: Ru: X –NH2: KOt-Bu = 100: 1: 1: 2 RACEMIZATION OF sec-ALCOHOLs: EFFECT OF AMINE LIGANDS [(hmb)RuCl2]2 Ru Cl Cl Cl Cl Ru NH2 OH NH2 NHTs 86 O2S NH2 OH 58 NH2 OH O SPh NH2 91 SH NHn-Bu 51 SH NMe2 99

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SLIDE 7

KOt-Bu toluene, 30 °C OH OH [(arene)RuCl2]2 arene ligand ee, % 94 99 >99% ee 24 h alcohol: Ru: amine: KOt-Bu = 100: 1: 1: 2 RACEMIZATION OF sec-ALCOHOLs: EFFECT OF ARENE LIGANDS [(arene)RuCl2]2 Ru Cl Cl Cl Cl Ru HS(CH2)2NH2 Rn Rn 99 68 92 7

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SLIDE 8

SYNTHESIS OF NOVEL unsym-DINUCLEAR µ-THIOLATO COMPLEX

P21/n (#14) R1(wR2)=0.055(0.164)

1H NMR (CDCl3) δ 2.18 (s, 18H), 1.98 (s, 18H) 13C NMR (CD3OD) δ 97.8, 97.7 (C6), 16.1, 15,9 (Me6)

ESI-TOFMS [C28H48ClN2Ru2S2]+ (m/z = 715) Ru Ru S Cl S N N + HS NH2 KOt-Bu 2-propanol reflux, 3 h 97% yield Ru: SN: KOt-Bu = 2: 2: 1 S Ru Ru S H2N Cl NH3 Ru Cl Cl Cl Cl Ru (Cl)2

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SLIDE 9

SYNTHESIS OF NOVEL unsym-DINUCLEAR µ-THIOLATO COMPLEXES

P21 (#4) R1(wR2)=0.040(0.101) Ru Ru S Cl S N N

+ HS NHR2 KOt-Bu 2-propanol reflux M: SN: KOt-Bu = 2: 2: 1 S M M S R2HN Cl NH2R2 M Cl Cl Cl Cl M (Cl)2 R1 R1 R1 R1 R2 % yield H H Ph H i-Pr H –(CH2)3– 97 89 93 63 H n-Bu 89 M (hmb)Ru Cp*Rh Cp*Ir H H Ph H H H Ph H –(CH2)3– 98 71 96 86 64

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SLIDE 10

EFFECT OF REACTION CONDITIONS

P-1 (#2) R1(wR2)=0.082(0.236) P-1 (#2) R1(wR2)=0.120(0.318) Ru Ru S N Ru N N S S

[(hmb)RuCl2]2 HS NH2 KOH 2-propanol 30 °C Ru Ru N S H Cl 68% yield CH3ONa THF 30 °C Ru H2N S S NH2 70% yield Ru: SN: base = 1: 2: 2 Ru: SN: base = 2: 1: 5 H

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SLIDE 11

SYNTHESIS OF sym-DINUCLEAR µ-THIOLATO COMPLEXES

1H NMR (CD3OD) δ 2.19 (s, 36H) 13C NMR (CD3OD) δ 98.4 (C6), 15,8 (Me6)

ESI-TOFMS [C29H48F3N2O3Ru2S3]+ (m/z = 829) P-1 (#2) R1(wR2)=0.065(0.149) Ru Ru S S N N CH2Cl2 –78 °C : r.t. Ru H2N S S NH2 MeOTf S Ru Ru S H2N NH2 (OTf)2 + MeS NH2 83% yield

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SLIDE 12

more active more active

RACEMIZATION WITH PREFORMED COMPLEXES

KOt-Bu toluene, 30 °C OH OH Ru cat >99% ee 1/2 [(hmb)RuCl2]2 HS(CH2)2NH2 base (1: 1: 1) 7% ee 24 h alcohol: Ru: KOt-Bu = 100: 1: 5 97% ee 83% ee 0% ee 0% ee S Ru Ru S H2N Cl NH3 (Cl)2 Ru Ru N S H Cl H Ru H2N S S NH2 S Ru Ru S H2N NH2 (OTf)2

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SLIDE 13

EFFECT OF BASE

KOt-Bu toluene, 30 °C OH OH 1 2 3 ee, % >99 >99 KOt-Bu/Ru2SN2, equiv 98 6 >99% ee alcohol: Ru = 100: 1 Ru2SN2 unsym-Ru2SN2 S Ru Ru S H2N Cl NH3 (Cl)2 S Ru Ru S H2N NH2 (OTf)2 sym-Ru2SN2 unsym (6 h) sym (3 h) 1 2 >99 >99 8

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SLIDE 14

GENERATION OF ACTIVE CATALYST

base 3 equiv base 2 equiv –HCl –HOTf S Ru Ru S H2N NH2 (OTf)2 S Ru Ru S H2N Cl NH3 (Cl)2 R1 R2 OH R1 R2 O R1 R2 O R1 R2 OH S NH Ru S NH2 H Ru S Ru Ru S HN NH Ru Ru N S H Cl Ru H2N S S NH2 H HS(CH2)2NH2 [(hmb)RuHCl]

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SLIDE 15

Ir Ir base S Ru Ru S H2N Cl NH3 (Cl)2 S NH Ru S S H2N Cl NH3 Ir S NH (Cl)2 base (Cl)2 (Cl)2 acid acid acid S Ir Ru S H2N Cl NH3 S S H2N Cl NH3 Ru Ir acid

CROSSOVER EXPERIMENTS

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SLIDE 16

FORMATION OF unsym-HETERODINUCLEAR µ-THIOLATO COMPLEXES

NaOH (excess) HCl aq. 2-propanol aq. ESI-TOFMS [C26H45ClN2IrRuS2]+ (m/z = 779)

1H NMR(CDCl3) δ 2.18 (18H), 1.60 (15H) <major>

1.97 (18H), 1.78 (15H) <minor> + S Ru Ru S H2N Cl NH3 (Cl)2 Ir Ir S S H2N Cl NH3 (Cl)2 (Cl)2 (Cl)2 S Ir Ru S H2N Cl NH3 S S H2N Cl NH3 Ru Ir + 2-propanol reflux (m/z = 715) (m/z = 843) NO REACTION

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SLIDE 17

ESI-TOFMS SPECTRA OF unsym-HETERODINUCLEAR COMPLEXES

found calcd m/z = 779

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SLIDE 18

EPIMERIZATION OF sec-ALCOHOLs WITH unsym-Ru2SN2

KOt-Bu toluene, 30 °C R1 R1 R2 OH R2 OH >99% ee alcohol: Ru: KOt-Bu = 100: 1: 1.5 unsym-Ru2SN2 unsym-Ru2SN2 S Ru Ru S H2N Cl NH3 (Cl)2 OH 6% ee (6 h) OH <1% ee (3 h) OH 11% ee (24 h) OH endo:exo = 57:43 (24 h)

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SLIDE 19

ISOMERIZATION OF ALLYLIC ALCOHOLs WITH unsym-Ru2SN2

toluene, 30 °C OH >99% yield (4 h) OH 93% yield (4 h) OH 91% yield (4 h) R1 R4 R3 R2 OH R1 R4 R3 R2 O alcohol: Ru: KOt-Bu = 100: 1: 1.5 unsym-Ru2SN2 S Ru Ru S H2N Cl NH3 (Cl)2 unsym-Ru2SN2 KOt-Bu OH >99% yield (1 h)

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SLIDE 20

base 3 equiv base 2 equiv –HCl –HOTf S Ru Ru S H2N NH2 (OTf)2 S Ru Ru S H2N Cl NH3 (Cl)2 R1 R2 OH R1 R2 O R1 R2 O R1 R2 OH S NH Ru S NH2 H Ru S Ru Ru S HN NH

SUMMARY

useful catalyst precursor for hydrogen transfer of alcohol