Organothorium-catalyzed hydroalkoxylation/cyclization of alkynyl alcohols. Scope, mechanism, and ancillary ligand effects

Stephen D. Wobser, Tobin J Marks

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Organothorium complexes bearing amide or alkyl proligands are active toward the highly selective hydroalkoxylation/cyclization of alkynyl alcohols. Substrates include primary and secondary alcohols, as well as terminal and internal alkynes. Catalysts with strongly binding ligation such as pentamethylcyclopentadienyl (Cp* = C5Me5) or "constrained geometry catalysts" (CGC = Me2Si(η 5-Me4C5)(tBuN)) remain soluble throughout the reaction, with the more sterically open (CGC)Th(NMe 2)2 (1) exhibiting higher activity than Cp*2Th(CH2TMS)2 (2). The use of precatalyst [(Me3Si)2N]2Th[κ2- (N,C)-CH2Si(CH3)2N(SiMe3)] (3) leads to precipitation upon the addition of alcohol substrates, although catalytic activity is retained. The substrate scope for 1 includes primary and secondary alcohols as well as terminal and internal alkynes. In situ1H NMR spectroscopic monitoring indicates that the rate law is zero-order in [substrate] and first-order in [catalyst]. The rates of primary alcohols and terminal alkynes are significantly more rapid than their more sterically hindered counterparts, suggesting that steric demands dominate the hydroalkoxylation/cyclization transition state. Turnover frequencies as high as 49 h-1 at 60 C are observed, producing exclusively the exo-methylene products. For internal alkyne substrates, alkenes with E-orientation are formed with complete selectivity. Activation parameters ΔH = 27.9(0.4) kcal/mol, ΔS = -3.0(1.1) eu, and E a = 28.6(0.4) kcal/mol are largely in accord with observations for other f-element-mediated insertive hydroelementation processes, and an ROH/ROD kinetic isotope effect of 0.97(0.02) is observed. The reactivity patterns, kinetics, and activation parameters are consistent with a pathway proceeding via turnover-limiting alkyne insertion into the Th-O bond, with subsequent, rapid Th-C protonolysis, regenerating the initial Th-OR species.

Original languageEnglish
Pages (from-to)2517-2528
Number of pages12
JournalOrganometallics
Volume32
Issue number9
DOIs
Publication statusPublished - May 13 2013

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Alkynes
Cyclization
alkynes
alcohols
Alcohols
Ligands
ligands
Substrates
catalysts
Catalysts
Bearings (structural)
Chemical activation
activation
Kinetics
kinetics
Alkenes
methylene
Amides
Isotopes
isotope effect

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Organothorium-catalyzed hydroalkoxylation/cyclization of alkynyl alcohols. Scope, mechanism, and ancillary ligand effects. / Wobser, Stephen D.; Marks, Tobin J.

In: Organometallics, Vol. 32, No. 9, 13.05.2013, p. 2517-2528.

Research output: Contribution to journalArticle

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abstract = "Organothorium complexes bearing amide or alkyl proligands are active toward the highly selective hydroalkoxylation/cyclization of alkynyl alcohols. Substrates include primary and secondary alcohols, as well as terminal and internal alkynes. Catalysts with strongly binding ligation such as pentamethylcyclopentadienyl (Cp* = C5Me5) or {"}constrained geometry catalysts{"} (CGC = Me2Si(η 5-Me4C5)(tBuN)) remain soluble throughout the reaction, with the more sterically open (CGC)Th(NMe 2)2 (1) exhibiting higher activity than Cp*2Th(CH2TMS)2 (2). The use of precatalyst [(Me3Si)2N]2Th[κ2- (N,C)-CH2Si(CH3)2N(SiMe3)] (3) leads to precipitation upon the addition of alcohol substrates, although catalytic activity is retained. The substrate scope for 1 includes primary and secondary alcohols as well as terminal and internal alkynes. In situ1H NMR spectroscopic monitoring indicates that the rate law is zero-order in [substrate] and first-order in [catalyst]. The rates of primary alcohols and terminal alkynes are significantly more rapid than their more sterically hindered counterparts, suggesting that steric demands dominate the hydroalkoxylation/cyclization transition state. Turnover frequencies as high as 49 h-1 at 60 C are observed, producing exclusively the exo-methylene products. For internal alkyne substrates, alkenes with E-orientation are formed with complete selectivity. Activation parameters ΔH‡ = 27.9(0.4) kcal/mol, ΔS‡ = -3.0(1.1) eu, and E a = 28.6(0.4) kcal/mol are largely in accord with observations for other f-element-mediated insertive hydroelementation processes, and an ROH/ROD kinetic isotope effect of 0.97(0.02) is observed. The reactivity patterns, kinetics, and activation parameters are consistent with a pathway proceeding via turnover-limiting alkyne insertion into the Th-O bond, with subsequent, rapid Th-C protonolysis, regenerating the initial Th-OR species.",
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N2 - Organothorium complexes bearing amide or alkyl proligands are active toward the highly selective hydroalkoxylation/cyclization of alkynyl alcohols. Substrates include primary and secondary alcohols, as well as terminal and internal alkynes. Catalysts with strongly binding ligation such as pentamethylcyclopentadienyl (Cp* = C5Me5) or "constrained geometry catalysts" (CGC = Me2Si(η 5-Me4C5)(tBuN)) remain soluble throughout the reaction, with the more sterically open (CGC)Th(NMe 2)2 (1) exhibiting higher activity than Cp*2Th(CH2TMS)2 (2). The use of precatalyst [(Me3Si)2N]2Th[κ2- (N,C)-CH2Si(CH3)2N(SiMe3)] (3) leads to precipitation upon the addition of alcohol substrates, although catalytic activity is retained. The substrate scope for 1 includes primary and secondary alcohols as well as terminal and internal alkynes. In situ1H NMR spectroscopic monitoring indicates that the rate law is zero-order in [substrate] and first-order in [catalyst]. The rates of primary alcohols and terminal alkynes are significantly more rapid than their more sterically hindered counterparts, suggesting that steric demands dominate the hydroalkoxylation/cyclization transition state. Turnover frequencies as high as 49 h-1 at 60 C are observed, producing exclusively the exo-methylene products. For internal alkyne substrates, alkenes with E-orientation are formed with complete selectivity. Activation parameters ΔH‡ = 27.9(0.4) kcal/mol, ΔS‡ = -3.0(1.1) eu, and E a = 28.6(0.4) kcal/mol are largely in accord with observations for other f-element-mediated insertive hydroelementation processes, and an ROH/ROD kinetic isotope effect of 0.97(0.02) is observed. The reactivity patterns, kinetics, and activation parameters are consistent with a pathway proceeding via turnover-limiting alkyne insertion into the Th-O bond, with subsequent, rapid Th-C protonolysis, regenerating the initial Th-OR species.

AB - Organothorium complexes bearing amide or alkyl proligands are active toward the highly selective hydroalkoxylation/cyclization of alkynyl alcohols. Substrates include primary and secondary alcohols, as well as terminal and internal alkynes. Catalysts with strongly binding ligation such as pentamethylcyclopentadienyl (Cp* = C5Me5) or "constrained geometry catalysts" (CGC = Me2Si(η 5-Me4C5)(tBuN)) remain soluble throughout the reaction, with the more sterically open (CGC)Th(NMe 2)2 (1) exhibiting higher activity than Cp*2Th(CH2TMS)2 (2). The use of precatalyst [(Me3Si)2N]2Th[κ2- (N,C)-CH2Si(CH3)2N(SiMe3)] (3) leads to precipitation upon the addition of alcohol substrates, although catalytic activity is retained. The substrate scope for 1 includes primary and secondary alcohols as well as terminal and internal alkynes. In situ1H NMR spectroscopic monitoring indicates that the rate law is zero-order in [substrate] and first-order in [catalyst]. The rates of primary alcohols and terminal alkynes are significantly more rapid than their more sterically hindered counterparts, suggesting that steric demands dominate the hydroalkoxylation/cyclization transition state. Turnover frequencies as high as 49 h-1 at 60 C are observed, producing exclusively the exo-methylene products. For internal alkyne substrates, alkenes with E-orientation are formed with complete selectivity. Activation parameters ΔH‡ = 27.9(0.4) kcal/mol, ΔS‡ = -3.0(1.1) eu, and E a = 28.6(0.4) kcal/mol are largely in accord with observations for other f-element-mediated insertive hydroelementation processes, and an ROH/ROD kinetic isotope effect of 0.97(0.02) is observed. The reactivity patterns, kinetics, and activation parameters are consistent with a pathway proceeding via turnover-limiting alkyne insertion into the Th-O bond, with subsequent, rapid Th-C protonolysis, regenerating the initial Th-OR species.

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