Mechanism of ruthenium-catalyzed hydrogen transfer reactions.: Concerted transfer of OH and CH hydrogens from an alcohol to a (cyclopentadienone)ruthenium complex

被引：115

作者：

Johnson, JB ^{[1
]}

Bäckvall, JE ^{[1
]}

机构：

[1] Stockholm Univ, Arrhenius Lab, Dept Organ Chem, SE-10691 Stockholm, Sweden

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 20期

关键词：

D O I：

10.1021/jo034634a

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Kinetic studies of the ruthenium-catalyzed dehydrogenation of 1-(4-fluorophenyl)ethanol (4) by tetrafluorobenzoquinone (7) using the Shvo catalyst 1 at 70 degreesC show that the dehydrogenation by catalytic intermediate 2 is rate-determining with the rate = k[4][1](1/2) and with DeltaHdouble dagger = 17.7 kcal mol(-1) and DeltaSdouble dagger = -13.0 eu. The use of specifically deuterated derivative 4-CHOD and 4-CDOH gave individual isotope effects of k(CHOH)/k(CHOD) = 1.87 +/- 0.17 and k(CHOH)/k(CDOH) = 2.57 +/- 0.26, respectively. Dideuterated derivative 4-CDOD gave a combined isotope effect of k(CHOH)/k(CDOD) = 4.61 +/- 0.37. These isotope effects are consistent with a concerted transfer of both hydrogens of the alcohol to ruthenium species 2.

引用

页码：7681 / 7684

页数：4

共 33 条

[1] X-RAY CRYSTAL-STRUCTURE DETERMINATION OF (PH4C4CO)(CO)2RU(NHET2) - A REACTIVE CATALYTIC INTERMEDIATE IN TRANSALKYLATION OF AMINES [J].

ABED, M ;

GOLDBERG, I ;

STEIN, Z ;

SHVO, Y .

ORGANOMETALLICS, 1988, 7 (09) :2054-2057

[2] Ruthenium(II)-catalyzed Oppenauer-type oxidation of secondary alcohols [J].

Almeida, MLS ;

Beller, M ;

Wang, GZ ;

Backvall, JE .

CHEMISTRY-A EUROPEAN JOURNAL, 1996, 2 (12) :1533-1536

[3] Ru(arene)(amino alcohol)-catalyzed transfer hydrogenation of ketones: Mechanism and origin of enantioselectivity [J].

Alonso, DA ;

Brandt, P ;

Nordin, SJM ;

Andersson, PG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (41) :9580-9588

[4]

[Anonymous], [No title captured]

[5] Kinetic isotope effect evidence for a concerted hydrogen transfer mechanism in transfer Hydrogenations catalyzed by [p-(Me2CH)C6H4Me]Ru-(NHCHPhCHPhNSO2C6H4-p-CH3) [J].

Casey, CP ;

Johnson, JB .

JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (05) :1998-2001

[6] Synthesis and reactivity of hydroxycyclopentadienyl and aminocyclopentadienyl ruthenium alcohol complexes [J].

Casey, CP ;

Vos, TE ;

Bikzhanova, GA .

ORGANOMETALLICS, 2003, 22 (05) :901-903

[7] Unexpected formation of the isopropylamine complex [2,3,4,5-Ph4(η4-C4CO)](CO)2Ru(H2NCHMe2) in the attempted synthesis of an isopropyl alcohol complex [J].

Casey, CP ;

Bikzhanova, GA ;

Bäckvall, JE ;

Johansson, L ;

Park, J ;

Kim, YH .

ORGANOMETALLICS, 2002, 21 (09) :1955-1959

[8] Hydrogen transfer to carbonyls and imines from a hydroxycyclopentadienyl ruthenium hydride: Evidence for concerted hydride and proton transfer [J].

Casey, CP ;

Singer, SW ;

Powell, DR ;

Hayashi, RK ;

Kavana, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (06) :1090-1100

[9] Efficient ruthenium-catalyzed aerobic oxidation of alcohols using a biomimetic coupled catalytic system [J].

Csjernyik, G ;

Éll, AH ;

Fadini, L ;

Pugin, B ;

Bäckvall, JE .

JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (05) :1657-1662

[10] MEERWEIN-PONNDORF-VERLEY REDUCTIONS AND OPPENAUER OXIDATIONS - AN INTEGRATED APPROACH [J].

DEGRAAUW, CF ;

PETERS, JA ;

VANBEKKUM, H ;

HUSKENS, J .

SYNTHESIS-STUTTGART, 1994, (10) :1007-1017

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