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Ruthenium Catalysed Oxidations of Organic Compounds by Ernest S

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Ruthenium Catalysed Oxidations of Organic Compounds by Ernest S Ruthenium Catalysed Oxidations of Organic Compounds By Ernest S. Gore Johnson Matthey Inc., West Chester, Pennsylvania Ruthenium and its complexes can be used to catalyse the oxidation, both homogeneous and heterogeneous, of a wide range of organic subs- trates. These include olefins, alkynes, arenes, alcohols, aldehydes, ketones, ethers, sulphides, amines, and phosphines. A wide variety of oxidants can be used under mild conditions; conversions and selectivities are usually high, and the catalyst can be easily recovered. Ruthenium can also be used to catalyse the oxidative destruction of pollutants in both gas and liquid phases. The synthetic use of ruthenium tetroxide as ruthenium tetroxide reactions (9). With the an oxidant for organic compounds was first emphasis shifting to ruthenium catalysed reac- reported in I 95 3 by Djerassi and Engle (I).The tions, new reactions have been discovered and scope of ruthenium oxidations was greatly conditions have been found which have expanded by Berkowitz and Rylander in 1958 improved the selectivity and yields of these (2). All of these early workers used ruthenium reactions. Thus it is appropriate to survey the tetroxide as a stoichiometric oxidant; however, subject again to summarise the state of the art. ruthenium tetroxide is rather inconvenient to use in this way. It is troublesome to prepare, Experimental Conditions expensive, and its strong oxidising power tends Many different ruthenium catalysts and to make it less selective than other oxidants. oxidants have been used. Of these, the most Caution-ruthenium tetroxide is an extremely common catalysts are RuCldPPhJ, powerful and volatile oxidant; it should only be RuCl,.xH,O, and RuO,.xH,O, and the most handled in a well ventilated area and when common oxidants are HOOAc, NaIO,, O,, and wearing appropriate protective clothing. NaOCl. Some catalysdoxidant systems are Thus it is not surprising that work was soon very selective indeed. For example both initiated on using ruthenium in catalytic RuCl,(PPh,)JPh(IOAc), and RuCl,(PPh),)@- quantities in oxidation reactions. The first such methylmorpholine-N-oxide specifically convert use of ruthenium seems to have been in an primary alcohols to aldehydes in high yields obscure publication in 1956 (3). A more readily (10, I I) and RuCl#Ph,)JPhCH=CHCOCH, available report appeared in 1959 (4). The converts vicinal diols to vicinal diketones (I2). advantages of catalytic ruthenium oxidations Conditions for ruthenium catalysed oxida- over stoichiometric ruthenium tetroxide have tions are very mild; usually a few hours or less proved to be so convincing that today virtually at room temperature is sufficient. A variety of all ruthenium mediated oxidations are perfor- solvent systems can be used, and depending on med catalytically. the oxidant a wide range of pH’s can be While several reviews (5-9) have been tolerated. Oxidations with oxygen can be written on ruthenium mediated oxidations, the carried out at atmospheric pressure. last one available in the West appeared ten Many ruthenium catalysed reactions have years ago and dealt equally with ruthenium been performed in the H,O-CCl, solvent system. catalysed reactions and stoichiometric But slow or incomplete reactions are platinum Melds Rev., 1983,27,(3), 111-125 111 occasionally encountered in this system, ruthenium as far as RuO,, which is insoluble. especially in the presence of carboxylic acids. Stronger oxidants such as NaOCl or NaIO, will Recently it has been found that adding CH3CN oxidise ruthenium to the +7 or +8 oxidation to the system greatly improves yields and reac- state and these are soluble. tion times (13, 14). When (Eh~decenewas The effect of the electronegativity of the sub- oxidised in HzO-CC1, only 20 per cent conver- stituent on the products of the oxidation of sion occurred in 2 hours; but on adding CHFN naphthalenes can be seen in reactions IV-F and the reaction was complete in the same period. IV-G. An electrondonating substituent favours cleavage of the substituted ring, while an Oxidation of Olefins electron-withdrawing substituent favours Cleavage of the Double Bond cleavage of the unsubstituted ring. When the oxidation of an olefin is catalysed Oxidation of Alcohols by ruthenium in the oxidation state +3 or higher, the usual result is cleavage of the double This is the most common synthetic use of bond. Ketones are produced if the carbons are ruthenium catalysed oxidations. Highly selec- fully substituted; otherwise acids, or tive conditions are readily available; alcohols occasionally, aldehydes are obtained, see Table can be converted to aldehydes rather than acids I. On the other hand, osmium tetroxide when and vicinal diols can be readily oxidised to used catalytically converts olefins to aldehydes either cleaved or non-cleaved products depend- rather than to acids (21). ing on conditions. In alcohols containing another oxidisable group such as a C=C double Non-Cleavage of the Double Bond bond, a CGC triple bond, an arene, nitrogen or Only a few non-cleavage reactions are sulphur, the hydroxyl group is oxidised pre- known, and these are given in Table 11. The ferentially (Table V). In substrates containing both primary and secondary alcohols the catalyst is usually a +2 ruthenium complex and the products are unpredictable. primary alcohol is oxidised preferentially, (see V-H). Oxidation of Alkynes Secondary Alcohols Terminal alkynes are cleaved to give acids These are oxidised cleanly and in good yields while internal alkynes yield diketones with no to ketones, see Table VI. Cyclobutanols can be cleavage, see Table 111. oxidised to cyclobutanones (38) (VI-F) in yields Oxidation of Arenes higher than with CrOJoxalic acid (39). Ruthenium catalysed oxidations of arenes Primary Alcohols can proceed in three ways, see Table IV: Primary alcohols are oxidised either to Alkyl side chains on the phenyl ring can be con- aldehydes (Table VII) or to acids (Table VIII). verted to-COOH (IV-A, B). The outcome of the reaction can be highly The phenyl ring can be cleaved from R-Ph to selective depending on the conditions used. For form R-COOH (IV-C, D). example: RuClXPPh,), with N- The phenyl ring can be degraded to form a methylmorpholine-N-xide (I I), O, (33), dicarboxylic acid (IV-E, F, G). PhCH=CHCOCH, (40) or Ph(IOAc), (10) In almost all cases where an alkyl side chain is always gives aldehydes. RuCIXPPhJ, with replaced by a carboxyl group, a heterogeneous excess PhIO (to), or RuC1, with HOOAc (42)or catalyst was used, for example IV-A, B. This is K&OR (32) always gives acids. one of the few cases in which a heterogeneous catalyst is used in ruthenium oxidations. Diols Oxygen is used as the oxidant since at Oxidation of diols can give either cleaved or temperatures below 4ooOC it can only oxidise non-cleaved products, see Table IX. Stronger Platinum Metals Rev., 1983,27, (3) 112 73 i? Table I P. f Oxidation of Olefins with Cleavage of the C = C Bond t Yield 2 Substrate Product Catalyst Oxidant Ref. c per cent 5 F CH3(CH,),CH = CH(CH,l,COOH CH,(CH,),COOH+ HOOC(CH,l,COOH RuO, NaOCl 94 c W m CH,(CH,),CH = CH, CH3(CH,),COOH RuCI, NalO, 89 W h) 21 h W v HOOC(CH,),,COOH RuO, 02 94 c c RuCI, 83 W NaOCl Ph' ph3Frh RuO, NalO, 62 PhCH = CH, PhCOOH RuO," 0, 92 PhCH = CH, PhCHO RuO, NalO, 82 f CHO Br Br RuO, NalO, 86 + Br Br "3 ppm cobalt naphthenate added Platinum Table II Oxidation of Olefins without Cleavage o the C = C Bond ield per cent Meto Substrate Product Catalyst Oxidant A CH,(CH,),CH = CH, Ru CI ,( PPh 3) , 0, 30,52 5 F c. RuCI,(PPh,) t-BuOOH 53 W B QcH = w, , m W h) 21 [Ru(trpv)(bipv) h C W (H,011 electricity - v 0 ’+ n 27 (conv.) RuCI, (PPh,), D 0, atio 1 :5:3 E RuCI, NalO, 51,12 +0AC OAc 40py+ Table I I I Oxidation of Alkvnes Substrate Product Catalyst Oxidant 00 NaOCl I1 II A PhC CPh PhCCPh 88 NaOCl I 70, 19 1 (26) B BuC CBu BuCCBu + BuCCOH Ruoz I C PhC E CH PhCOOH RuO, NaOCl 66 (26) D ‘Buck CH ‘BUCOOH I NaOCl I 60 I (26) E HCE CCH(NH,)CH,CH,COOH HOOCCH(NH,)CH,CH,COOH RuO, NalO, 50 (27) 5 P -2 Q Q m m * 0 0 (9 cn W l- sr: r-- u u % P z I I 0 0 Arenes IV of '6 Table u z & I+ I I+ I 00 Oxidation 00 V 0 88 88 0 I 0 0 I bI b1 J- 0 U m 0 n Yatinum Metals Rev., 1983, 27, (3) 115 I > C d I- (D I- In Q) 8' 0) Q) (D d (0 Ic -In 0 I- Groups n r n n -n N s K Functional s K Other of n 1n I V V +- 2, 2, I V Tabie the Presence the in 0/ .'t Alcohols Q 0I of ON I 0 5I Oxidation I Selective +- 0 I I =N 0, 0 I I v)L >c 0I n d I0%i U m u 0 w LL (1 I Platinum Metals Rev., 1983,27, (3) 116 - hl I- hl zi W m -m - s 1m s Lo W 7 0 Lo OD m OD b OD 0) I- P 9 4 4 0m nc Y Y z n 2 Qa K Qa Alcohols I VI 0 Secondary Table of 0d' Oxidation a m u n w LL Platinum Metals Rev., 1983,27, (3) 117 Table VII Platinum Oxidation of Primarv Alcohols to Aldehydes Substrate Product Catalyst Oxidant field per cent A CH,(CH,),CH,OH CH,(CH,),CHO RuCI,( PPh,), Metals nPH3 90 3 wN\o 5 0 RuCI,(PPh,), 79 F %CHO 3 c.
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