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A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
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In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
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Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
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Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
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Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Ruthenium catalysed C-H bond borylation.

José A Fernández-Salas1, Simone Manzini, Lorenzo Piola

  • 1EaStCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK. snolan@st-andrews.ac.uk.

Chemical Communications (Cambridge, England)
|May 20, 2014
PubMed
Summary

Ruthenium complexes catalyze ortho-selective borylation of pyridyl substrates. This novel ruthenium(IV)-catalyzed C-H activation reaction achieves high yields with low catalyst loadings.

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Organic Synthesis

Background:

  • Ruthenium complexes are versatile catalysts in organic synthesis.
  • C-H activation and borylation are key transformations for functionalizing organic molecules.
  • Developing efficient catalytic systems for selective borylation is an ongoing challenge.

Purpose of the Study:

  • To synthesize novel phenylindenyldihydridosilyl ruthenium complexes.
  • To investigate the catalytic activity of these complexes in the ortho-selective borylation of pyridyl substrates.
  • To explore a new ruthenium(IV)-catalyzed C-H activation borylation/functionalization reaction.

Main Methods:

  • Reaction of tertiary silanes with [RuCl(3-phenylindenyl)(PPh3)2].
  • Catalytic testing of the synthesized ruthenium complexes for borylation reactions.
  • Optimization of reaction conditions to achieve high selectivity and yield.

Main Results:

  • Easily prepared phenylindenyldihydridosilyl ruthenium complexes were synthesized.
  • The [RuH2(3-phenylindenyl)(SiEt3)] complex demonstrated high efficiency (1.5 mol%) in ortho-selective pyridyl borylation, achieving yields up to 90%.
  • A novel ruthenium(IV)-catalyzed C-H activation borylation/functionalization reaction was successfully developed.

Conclusions:

  • Novel ruthenium complexes can be readily prepared.
  • The developed catalytic system enables highly efficient and selective ortho-borylation of pyridyl substrates.
  • This study presents a new pathway for C-H activation borylation/functionalization using low ruthenium catalyst loadings.