( - a r e n e ) R u - PowerPoint PPT Presentation

アミ ノ チオール配位子をも つ ( - a r e n e ) R u 錯体の合成と その触媒機能 η 6 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 0 6

Cp*Ru(AMINE) CATALYSTS FOR RACEMIZATION OF CHIRAL sec -ALCOHOLs OH O R 1 R 2 R 1 R 2 Ru Ru L H L N NH H H OH O R 1 R 2 R 2 R 1 Ph 2 Me 2 P N Ru Ru N N Cl Cl H 2 H 2 inactive highly active up to 479 TOF/h Conditions: Ru + KO t -Bu (1:1), [alcohol] = 0.1 – 1.0 M in toluene, 30 ºC Tetrahedron Lett. 2003 , 44 , 7521

OXIDATIVE TRANSFORMATION OF ALCOHOLs WITH Cp*Ru(PN) CATALYSTS intramolecular hydrogen transfer of allylic alcohols: concise synthesis of muscone O R 3 R 3 R 3 OH O O – H 2 + H 2 R 1 R 4 R 1 R 4 R 1 R 4 R 2 R 2 R 2 >2500 TOF/h at 30 °C muscone J. Am. Chem. Soc. 2005 , 127 , 6172 intrermolecular hydrogen transfer from diol to acetone: synthesis of γ -lactones O O O OH – H 2 – H 2 CH 2 OH O O O OH OH OH >1000 TOF/h at 30 °C n- C 12 H 25 muricatacin Org. Lett. 2007 , 9 , 1821

ISOELECTRONIC Ru–AMINE COMPLEXES X L Ru Ru N N Cl Cl H 2 H 2 Me 2 Ts N N O Ru Ru Ru N N N Cl Cl Cl H 2 H 2 H 2 Ph 2 P S Cl n ( ) Ru Ru Ru N N N Cl Cl Cl H 2 H 2 H 2

( η 6 -arene)Ru(AMINE) CATALYSTS FOR CHEMOENZYMATIC ASYMMETRIC SYNTHESIS OH OH Ts N Ru Ru + KOH (1 mol%) N 70 °C, 48 h Cl H 2 >99% ee 0% ee R. A. Sheldon Tetrahedon: Asymmetry , 2002 , 13 , 879. O O H O ROH N O O n OR Ru Ru + base n N Cl Novozym 435 Ph H 2 0% ee 92% ee (n = 5) A. R. A. Palmans J. Am. Chem. Soc , 2005 , 127 , 9964. A. Heise, Angew. Chem. Int. Ed. 2006 , 45 , 2130.

RACEMIZATION OF sec- ALCOHOLs: EFFECT OF AMINE LIGANDS OH OH [(hmb)RuCl 2 ] 2 X –NH 2 Cl Cl KO t- Bu Ru Ru toluene, 30 °C Cl Cl 24 h >99% ee alcohol: Ru: X –NH 2 : KO t- Bu = 100: 1: 1: 2 [(hmb)RuCl 2 ] 2 NHTs OH OH O OH O 2 S X –NH 2 ligand NH 2 NH 2 NH 2 NH 2 ee, % 76 14 86 58 SH SH SH SPh NH 2 NH n -Bu NMe 2 NH 2 7 51 99 91

RACEMIZATION OF sec- ALCOHOLs: EFFECT OF ARENE LIGANDS OH OH [(arene)RuCl 2 ] 2 R n HS(CH 2 ) 2 NH 2 Cl Cl KO t- Bu Ru Ru toluene, 30 °C R n Cl Cl 24 h >99% ee alcohol: Ru: amine: KO t- Bu = 100: 1: 1: 2 [(arene)RuCl 2 ] 2 arene ligand ee, % 99 94 99 92 68 7

SYNTHESIS OF NOVEL unsym -DINUCLEAR µ -THIOLATO COMPLEX NH 3 (Cl) 2 H 2 N Cl Cl Cl KO t- Bu S + Ru Ru HS NH 2 Ru Ru 2-propanol Cl Cl S reflux, 3 h Ru: SN: KO t -Bu = 2: 2: 1 97% yield Cl 1 H NMR (CDCl 3 ) δ 2.18 (s, 18H), 1.98 (s, 18H) 13 C NMR (CD 3 OD) δ 97.8, 97.7 ( C 6 ), 16.1, 15,9 ( Me 6 ) N S N ESI-TOFMS [C 28 H 48 ClN 2 Ru 2 S 2 ] + ( m/z = 715) Ru Ru S P 2 1 / n (#14) R 1(w R 2)=0.055(0.164)

SYNTHESIS OF NOVEL unsym -DINUCLEAR µ -THIOLATO COMPLEXES R 1 NH 2 R 2 (Cl) 2 R 1 R 2 HN Cl Cl Cl KO t- Bu R 1 S + M M NHR 2 HS M M 2-propanol Cl Cl S reflux M: SN: KO t -Bu = 2: 2: 1 R 1 R 2 M % yield (hmb)Ru H H 97 Cl Ph H 93 N S N i- Pr H 89 Ru Ru H n- Bu 89 –(CH 2 ) 3 – 63 S Cp*Rh H H 98 Ph H 71 Cp*Ir H H 96 P 2 1 (#4) Ph H 86 R 1(w R 2)=0.040(0.101) –(CH 2 ) 3 – 64

EFFECT OF REACTION CONDITIONS Cl [(hmb)RuCl 2 ] 2 CH 3 ONa KOH H N S Ru NH 2 H 2 N 2-propanol THF S Ru Ru 30 °C 30 °C H S HS NH 2 70% yield 68% yield Ru: SN: base = 1: 2: 2 Ru: SN: base = 2: 1: 5 S Ru Ru Ru N N S N S P- 1 (#2) P- 1 (#2) R 1(w R 2)=0.120(0.318) R 1(w R 2)=0.082(0.236)

SYNTHESIS OF sym -DINUCLEAR µ -THIOLATO COMPLEXES (OTf) 2 H 2 N MeOTf S NH 2 Ru + NH 2 Ru Ru MeS H 2 N CH 2 Cl 2 S S –78 °C : r.t. S NH 2 83% yield N 1 H NMR (CD 3 OD) δ 2.19 (s, 36H) S 13 C NMR (CD 3 OD) δ 98.4 ( C 6), 15,8 ( Me 6) Ru Ru ESI-TOFMS [C 29 H 48 F 3 N 2 O 3 Ru 2 S 3 ] + ( m/z = 829) S N P- 1 (#2) R 1(w R 2)=0.065(0.149)

RACEMIZATION WITH PREFORMED COMPLEXES OH OH Ru cat 1/2 [(hmb)RuCl 2 ] 2 KO t- Bu HS(CH 2 ) 2 NH 2 toluene, 30 °C base (1: 1: 1) 24 h >99% ee 7% ee alcohol: Ru: KO t -Bu = 100: 1: 5 NH 3 (Cl) 2 (OTf) 2 H 2 N Cl H 2 N S S Ru Ru Ru Ru S S NH 2 0% ee 0% ee more active more active Cl H N S Ru Ru Ru NH 2 H 2 N S H S 83% ee 97% ee

EFFECT OF BASE OH OH Ru 2 SN 2 KO t- Bu toluene, 30 °C >99% ee alcohol: Ru = 100: 1 NH 3 (Cl) 2 H 2 N Cl KO t- Bu / Ru 2 SN 2 , equiv S Ru Ru unsym (6 h) sym (3 h) ee, % S 0 >99 unsym- Ru 2 SN 2 1 >99 2 98 (OTf) 2 3 6 H 2 N 0 >99 S Ru Ru 1 >99 S NH 2 2 8 sym- Ru 2 SN 2

GENERATION OF ACTIVE CATALYST (OTf) 2 NH 3 (Cl) 2 H 2 N Cl HN H 2 N –HCl –HOTf S S S Ru Ru Ru Ru Ru Ru base base S S S 3 equiv 2 equiv NH NH 2 Cl H N S OH O Ru Ru R 1 R 2 R 1 R 2 H [(hmb)RuHCl] Ru Ru S H S NH NH 2 Ru NH 2 HS(CH 2 ) 2 NH 2 H 2 N OH O S S R 1 R 2 R 2 R 1

CROSSOVER EXPERIMENTS NH 3 NH 3 (Cl) 2 (Cl) 2 H 2 N Cl H 2 N Cl S S Ir Ir Ru Ru NH 3 S S (Cl) 2 H 2 N Cl S Ru Ir S acid acid base base acid acid NH 3 (Cl) 2 H 2 N Cl S Ir Ru Ru Ir S S S NH NH

FORMATION OF unsym -HETERODINUCLEAR µ -THIOLATO COMPLEXES NH 3 NH 3 (Cl) 2 (Cl) 2 H 2 N H 2 N Cl Cl S S Ru Ir Ru ( m/z = 715) Ru S S NaOH (excess) HCl aq. + + 2-propanol aq. NH 3 NH 3 (Cl) 2 (Cl) 2 H 2 N H 2 N Cl Cl S S Ir Ir Ru Ir ( m/z = 843) S S 2-propanol ESI-TOFMS [C 26 H 45 ClN 2 IrRuS 2 ] + ( m/z = 779) reflux 1 H NMR(CDCl 3 ) δ 2.18 (18H), 1.60 (15H) <major> 1.97 (18H), 1.78 (15H) <minor> NO REACTION

ESI-TOFMS SPECTRA OF unsym -HETERODINUCLEAR COMPLEXES m/z = 779 found calcd

EPIMERIZATION OF sec -ALCOHOLs WITH unsym -Ru 2 SN 2 NH 3 (Cl) 2 unsym- Ru 2 SN 2 H 2 N OH OH Cl KO t- Bu S Ru Ru toluene, 30 °C R 1 R 2 R 1 R 2 S >99% ee unsym- Ru 2 SN 2 alcohol: Ru: KO t- Bu = 100: 1: 1.5 OH OH 6% ee (6 h) <1% ee (3 h) OH OH 11% ee (24 h) endo:exo = 57:43 (24 h)

ISOMERIZATION OF ALLYLIC ALCOHOLs WITH unsym -Ru 2 SN 2 NH 3 (Cl) 2 R 3 R 3 unsym- Ru 2 SN 2 H 2 N OH O Cl KO t- Bu S Ru Ru R 1 R 4 R 1 R 4 toluene, 30 ° C S R 2 R 2 unsym- Ru 2 SN 2 alcohol: Ru: KO t- Bu = 100: 1: 1.5 OH OH >99% yield (1 h) 91% yield (4 h) OH OH >99% yield (4 h) 93% yield (4 h)

SUMMARY NH 3 (Cl) 2 (OTf) 2 H 2 N Cl HN H 2 N –HCl –HOTf S S S Ru Ru Ru Ru Ru Ru base base S S S 3 equiv 2 equiv NH NH 2 OH O R 1 R 2 R 1 R 2 Ru Ru S H S NH NH 2 OH O useful catalyst precursor for R 1 R 2 R 2 R 1 hydrogen transfer of alcohol