Smarium(II) Iodide (SmI2)

 SmI2 is air sensitive and should be handled under inert atmosphere.

 It may be stored over THF for longer period.

Barbier-Type Reactions

 SmI2 is quite useful in promoting Barbier-type reactions between aldehydes or

ketones and a variety of organic halides.

 The reaction time and temperature can be reduced by adding catalytic

amount of FeCl3 or HMPA.

 For example, annulations of six member ring occur with excellent

diastereoselectivity via an intramolecular Barbier-type reaction in the

presence of catalytic FeCl3 at mild conditions.

Pinacolic Coupling Reactions

 Both aldehydes and ketones are coupled in the presence of SmI 2 to give

pinacol.
Radical Addition to Alkenes and Alkynes

SmI2 can mediate the cyclization of aryl radicals onto alkene and alkyne acceptors to

give an excellent route to the synthesis of heterocycles.

Reduction Reactions

 SmI2 reduces alkyl halides to give hydrocarbons in the presence of proton

source.

Nucleophilic Acyl Substitutions

 In the presence of catalytic FeCl3 at mild conditions can be used to facilitate

the selective intramolecular acyl substitution of halo esters.

 Unlike the organolithium reagents, SmI-promoted nucleophilic substitutions

don't proceed with double addition to the carbonyl.

Ketone-Alkene Coupling Reactions

 Ketyl radicals generated from reduction of ketones or aldehydes with SmI 2

can be coupled both inter- and intra-molecularly to a variety of alkenic

species.

 For example, ketone-alkene cyclization can be pursued in a stereocontrolled

manner.
RuO2

 Ruthenium(IV) oxide (RuO2) is a black chemical compound containing the

rare metal ruthenium and oxygen.

 RuO2 is generally used as a catalyst in various industrial applications or an

electrode in electrochemical processes.

 RuO2 is highly reactive with reducing agents, due to its oxidizing properties.

 It has rutile crystal structure, similar to titanium dioxide and several other

metal oxides.

 Due to its structure, ruthenium(IV) oxide easily forms hydrates.

Preparation

 It is usually prepared by oxidation of ruthenium trichloride.

 The single crystals of RuO2 can be obtained by chemical vapor transport,

using O2 as the transport agent.

RuO2 + O2 ⇌ RuO4

Oxidative Catalyst

 RuO2 by itself is a poor catalyst because without the presence of a hydrate its

surface area is greatly decreased.

 To get pure ruthenium(IV) oxide, it needs to be annealed at 900ºC.

 The best catalyst for electrochemical processes is to have some hydrate

present, but not a completely hydrous one.

 RuO2 can be used as catalyst in many other situations. Important reactions are

the Fischer-Tropsch process, Haber–Bosch process, and various

manifestations of fuel cells.

 RuO2 is used as the main component in the catalyst of the Sumitomo-Deacon

process which produces chlorine by the oxidation of hydrogen chloride.

Ru-BINAP Complex (Noyori Catalysts or Noyori Asymmetric Hydrogenation)

 Noyori is most famous for asymmetric hydrogenation using as catalysts

complexes of rhodium and ruthenium, particularly those based on the BINAP

ligand.

 Asymmetric hydrogenation of an alkene in the presence of ((S)-

BINAP)Ru(OAc)2 is used for the commercial production of enantiomerically

pure naproxen, used as an anti-inflammatory drug.

 The antibacterial agent levofloxacin is manufactured by asymmetric

hydrogenation of ketones in the presence of a Ru(II)-BINAP halide complex.

Mechanism
Industrial Applications

 Noyori-inspired hydrogenation catalysts have been applied to the commercial

synthesis of number of fine chemicals.

 (R)-1,2-Propandiol, precursor to the antibacterial levofloxacin, can be

efficiently synthesized from hydroxyacetone using Noyori asymmetric

hydrogenation.

 An antipsychotic agent BMS 181100 is synthesized using BINAP/diamine-Ru

catalyst.
Platinum (PtO2, Adam’s Catalyst)

 Adams' catalyst whose chemical name is platinum dioxide, is represented as

platinum(IV) oxide hydrate (PtO2.H2O).

 This catalyst is used in hydrogenolysis and hydrogenation in organic

synthesis.

 The oxide itself is not an active catalyst, but it becomes active after exposure

to hydrogen whereupon it converts to platinum black, which is responsible

for reactions.

Preparation

 It is prepared from chloroplatinic acid H2PtCl6, by fusion with sodium nitrate.

H2PtCl6 + 6 NaNO3 → Pt(NO3)4 + 6 NaCl (aq) + 2 HNO3

Pt(NO3)4 → PtO2 + 4 NO2 + O2

Applications

 Adams' catalyst is used for many applications. It has shown to be valuable for

hydrogenation, hydrogenolysis, dehydrogenation, and oxidation reactions.

 Hydrogenation occurs with syn stereochemistry when used on an alkene

resulting in an alkane.

 Some of the most important transformations include the hydrogenation of

ketones to alcohols and the reduction of nitro compounds to amines.

 However, reductions of alkenes can be performed with Adam's catalyst in the

presence of nitro groups without reducing the nitro group.

 When reducing nitro compounds to amines, platinum catalysts are preferred

over palladium catalysts to minimize hydrogenolysis.

  The catalyst is also used for the hydrogenolysis of phenyl phosphate esters, a

reaction that does not occur with palladium catalysts. The pH of the solvent

significantly affects the reaction course, and reactions of the catalyst are often

enhanced by conducting the reduction in neat acetic acid, or solutions of

acetic acid in other solvents.

 The reduction of the dihydropyrroleoccurs with good selectivity using PtO2

catalyst.

 The reduction of the 1,2-dimethyl cyclohexene to cis-1,2-dimethyl cyclohexane

using PtO2 catalyst.

Examples: