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Volumn 131, Issue 3, 2009, Pages 1077-1091

Mechanistic insights into the rhodium-catalyzed intramolecular ketone hydroacylation

Author keywords

[No Author keywords available]

Indexed keywords

[CARBONYL; AS-LIGANDS; BOND FORMING; C-H BOND; CH-BOND ACTIVATION; CHIRAL LIGAND; DECARBONYLATION; DENSITY FUNCTIONAL THEORY CALCULATIONS; DETAILED KINETICS; DOUBLE BONDS; ENANTIOMERIC EXCESS; ENERGY TRANSITION STATE; EXPERIMENTAL DATA; HAMMETT PLOTS; HYDROACYLATION; INDUCTION PERIODS; INTRAMOLECULAR HYDROACYLATION; KINETIC ISOTOPE EFFECTS; KINETICS SIMULATIONS; LIMITING STEP; LONE PAIR; MECHANISTIC PATHWAYS; MODEL-BASED; OXIDATIVE ADDITIONS; PRECATALYST; PRODUCT INHIBITION; REDUCTIVE ELIMINATION; RHODIUM CARBONYL SPECIES; RHODIUM HYDRIDES; RHODIUM-CATALYZED; SEGPHOS; THEORETICAL STUDY; TRANSITION STATE STRUCTURE; TRANSITION-STATE;

EID: 67749119978     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja806758m     Document Type: Article
Times cited : (118)

References (75)
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    • At the B3LYP/lan2ldz level of theory see Computational Study for details
    • At the B3LYP/lan2ldz level of theory (see Computational Study for details).
  • 42
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    • The same result was obtained when 2a and 2h were used. Here three doublets were observed, (6 25.8, J(Rh-P) = 192 Hz; δ 22.1, J(Rh- P) = 191 Hz; δ 21.9, J(Rh-P) = 190 Hz); however, the two upheld doublets are present when only 2h is added, and thus are likely two binding modes of 2h.
    • The same result was obtained when 2a and 2h were used. Here three doublets were observed, (6 25.8, J(Rh-P) = 192 Hz; δ 22.1, J(Rh- P) = 191 Hz; δ 21.9, J(Rh-P) = 190 Hz); however, the two upheld doublets are present when only 2h is added, and thus are likely two binding modes of 2h.
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    • At 0 °C, a small amount 3, of an unidentified species was observed in the 31P NMR spectrum
    • 31P NMR spectrum.
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    • Three-coordinate Rh(I) have been reported in the literature: (a) Yared, Y. W.; Miles, S. L.; Bau, R.; Reed, C. A. J. Am. Chem. Soc. 1977, 99, 7067.
    • Three-coordinate Rh(I) have been reported in the literature: (a) Yared, Y. W.; Miles, S. L.; Bau, R.; Reed, C. A. J. Am. Chem. Soc. 1977, 99, 7067.
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    • It is also possible that reversible insertion steps could lead to a pre- equilibrium isotope effect which would translate to different rates of rate-limiting reductive elimination based on different concentrations of the intermediate prior to reductive elimination. However, we believe this is unlikely since the observed κH/κ D, 1.8 is large for a thermodynamic isotope effect:(a) Kogut, E, Zeller, A, Warren, T. H, Strassner, T. J. Am. Chem. Soc. 2004, 126, 11984 Also see Computational Study for additional support for ketone insertion as the rate- determining step
    • D = 1.8 is large for a thermodynamic isotope effect:(a) Kogut, E.; Zeller, A.; Warren, T. H.; Strassner, T. J. Am. Chem. Soc. 2004, 126, 11984 Also see Computational Study for additional support for ketone insertion as the rate- determining step.
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    • D = 3.3 ± 0.3 was determined for the same substrate with [Rh(R)-DTBM-SEGPHOS](BF4).
    • D = 3.3 ± 0.3 was determined for the same substrate with [Rh(R)-DTBM-SEGPHOS](BF4).
  • 53
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    • Of note, when the tBu-substituted ketone 1k was added (20 equiv) to a solution of Rh((R)-DTBM-SEGPHOS)]BF4 in CD2Cl 2, the spectrum showed only one doublet δ 39.1, J, 201 Hz, We believe the steric bulk of the tBu group prevents coordination of a second equivalent of substrate
    • 2, the spectrum showed only one doublet (δ 39.1, J = 201 Hz). We believe the steric bulk of the tBu group prevents coordination of a second equivalent of substrate.
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    • See Supporting Information for a discussion of how Keq can be estimated by two complementary methods
    • See Supporting Information for a discussion of how Keq can be estimated by two complementary methods.
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    • See Supporting Information for a rate law describing substrate and product dependences
    • See Supporting Information for a rate law describing substrate and product dependences.
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    • Substrate 1t was inadvertantly synthesized via a Swern oxidation of the keto-alcohol precursor of 1s. See Supporting Information for details.
    • Substrate 1t was inadvertantly synthesized via a Swern oxidation of the keto-alcohol precursor of 1s. See Supporting Information for details.
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