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567
568 Chemical Reviews, 1974, Vol. 74, NO.5 G. Brieger and T. J. Neslrick
TABLE I. Hydrogen Donor Compounds TABLE ll.14 Reduction of Cinnamic Acid in the Presence of
Compound Catalyst Ref Various D o n o w
TABLE IV.2"34 Effect of Substitution in Cyclohexene on TABLE V.14 Effect of Solvent on Transfer Hydrogenation of
Donor Activity" p-Methoxycinnamic Acida
Reaction
Solvent Bp, "C time, min
% succinic % hydrocin- p-Cy me ne 175 1
acid namic acid % P' p- Ment ha ne 170 1
R after 48 hr after 72 hr toluidine Mesitylene 165 3
H 96.3 100 95 Xylene 140 10
CHa 75 50 Toluene 111 90
CH3CH2 34 15 4.85 Toluene -+ benzene 102 330
(CH3)zC H 24 4 0 Toluene + benzene 90 2760
CHdCHA 24.5 2.5 2.13 Isovaleric acid 176 1
Cyclo hexyl 10 Trace 2.19 Isobutyric acid 154 1
Phenyl 50 34.5 9.35 Acetic acid 118 20
p- Met hy Ia ni so le 177 1
'IReaction conditions: 0.01 mol of maleic or cinnamic acid; 0.02 mol Phenyl methyl ether 154 5
of donor: 50 rng of 5% Pd/C; 25 rnl of THF, reflux; 0.0167 mol ofp-nitro-
toluene; 0.05 mol of donor; 100 m g of 5% Pd/C; 82". Hexanol 156 10
N,N-Dimethylaniline 193 10
N,N-Dimethylcyclohexylamine 162 20
ing bulk of the substituent clearly reduces the rate of
a Reaction conditions: 0.0025 mol ofp-methoxycinnamic acid; 0,0368
reaction, whereas activating substituents such as phenyl mol of d-limonene; 0.4 g 5% Pd/C; 20 rnl of solvent refluxed until
increase the rate again. The interesting question is raised quantitative reduction occurred.
here whether this effect is due to participation of the
donor in the hydrogen transfer step or whether the differ-
ence simply reflects the relative ease of dehydrogenation TABLE Vl.31,48Effect of Solvent on Transfer Hydrogenation
of the various cyclohexenes. That the former is more of p-Nitrotoluene
likely may be inferred from the fact that after 48 hr uhder Yield of p-toluidine,%
the same conditions, but without an acceptor, cyclohex- Solvent BP, "C a b
ene, 1-ethylcyclohexene, and 1-phenylcyclohexene are
Xylene 120 49.8
essentially completely d e h y d r ~ g e n a t e d . ~ ~
Toluene 105 20.75
Benzene 104 28.25 73< (16)
6. Effect of Solvents Cyclohexane 85 4.7 75
The effect of solvents on the course of the reaction Acetic acid 118 55
has been studied in a limited number of cases. These re- Acetone 60 4.15 90
sults are presented in Table v. Greater sensitivity to the Tetra hydrofuran 70 55.6 85
Diethyl ether 39 0 55
nature of the solvent is shown in the reduction of nitro
Methanol 56 0
compounds. This is shown in Table V I . The special effec-
Ethanol 80 9.6 77
tiveness of tetrahydrofuran was noted by Gaiffe and Plo-
t i a ~ , ~but
' the results of Braude, et suggest that " Reaction conditions: 0.05 mol of cyclohexene donor; 0.067 mol of
such large differences between solvents do not exist. p-nitrotoluene acceptor; 100 mg ot 5% Pd/C; 50 ml of solvent, re-
fluxed 24 hr. '' Reaction conditions: 0.056 mol of cyclohexene donor;
Use of a more effective donor such as a-phellandrene 0.0182 mol ofp-nitrotoluene acceptor; 20 mg of Pd black; 50 ml of sol-
raises the yields of p-toluidine to 9 5 ' 3 0 . ~ ~ vent refluxed 17 hr. "The higher yield is obtained with benzene puri-
The effect of solvent on the system cinnamic acid ac- fied by refluxing with Raney nickel and distillation.
ceptor-a-phellandrene donor was also studied. l 4 The
following general conclusions seem warranted. Below a compound was not reduced, and the evolution of free hy-
critical temperature, dependent on the donor (ca. 90" for drogen greatly decreased. Similarly, Braude, et a/., noted
limonene), little or no hydrogen transfer occurs. Above the inhibitory effect of an aldehyde group in the reduction
this threshold temperature, the reaction rate increases of n i t r ~ b e n z a l d e h y d e s . These
~~ functional groups would
rapidly and appears to be independent of the nature of therefore be disadvantageous in a solvent. Within these
the solvent as far as hydrocarbons, acids, or ethers are limits, a wide range of solvents, including carboxylic
involved. Alcohols and amines, which have the capability acids, can be used.
of reacting themselves with the catalyst (see below), ap-
pear to retard the reaction somewhat. C. Effect of Temperature
When using alcohols as solvents, it must be consid-
ered that these can also serve as hydrogen donors, espe- As was noted above, temperature appears to be a very
cially when Raney nickel is used as catalyst.40 I t is there- critical variable for catalytic transfer hydrogenation. In-
fore possible that hydrogen transfer takes place from sol- deed at higher temperatures, in the range 300-350°, hy-
vent to donor, thereby reducing the reaction rate. Amines drogen transfers can be used to hydrogenate beneene to
are also dehydrogenated by Raney n i ~ k e I , ~ and ~ - ~ 'a cyclohexane as mentioned earlier.p3 Generally such reac-
similar problem may occur. tions have been used for aromatization, however, rather
The possibility of a competitive inhibition by certain than to effect hydrogenation. An example of such a reac-
functional groups seems to have been observed early by tion is shown below in eq 2.
Kindler and P e ~ c h k e They
. ~ ~ noted that p-nitrocinnamic I I
acid was not reduced by a-phellandrene under conditions
which readily reduced p-methoxycinnamic acid. A certain
amount of free hydrogen gas is nevertheless evolved dur-
ing the reaction. When p-nitrocinnamic acid and p -
methoxycinnamic acid were combined, the methoxy
570 Chemical Reviews, 1974, Vol. 74, No. 5 G. Brieger and T. J. Nestrick
TABLE VII. Catalysts for Transfer Hydrogenation TABLE V111.48 Comparison of Catalysts for Transfer
Catalyst Ref Hydrogenation“ of p-Nitrotoluene
~
Yield of
Pd black 4, 5, 6, 32
Amount Time, p-toluidine,
P’dI C 8, 14-16, 19-22, 24-39, 42-46, 48 Catalyst mg hr %
Pd/alumina 41
Ni/al umi na 23 10% Pd/C 190 7 95
Ni/Kieselgur I 1%Pd/CaC08 100 18 95
Raney nickel 40, 49-51 0.1% Pd/A1203 1000 18 64
RuCl*(PhaP)a 12, 13 PdC12 20 17 1
I r H C12(M e2SO)a 10, 11 Pd/Pt* 10 13 100
IrBr(CO)(Ph3P)a 13 Pt black 20 7 18
R hCI(Ph8P)a 13 10% Pt/C 350 7 13
+
PtCI2(PhaAs)? SnCI2,H20 9 PtOz
Raney nickel
45
100
17
22
0
2
D. Effect of Catalyst W 7 Raney nickel 100 100 2
A number of different catalysts have been utilized for a Reaction conditions: 2.5 g ofp-nitrotoluene; 15 ml of cyclohexene;
catalytic hydrogen transfer reactions. Some of the early
*
catalyst as per table; time reflux as per table. Pd deposited elec-
trolytically on platinum foil.
discrepancies in these studies were undoubtedly due to
subtle differences in catalyst preparation. The catalysts stance, palladium is much more effective than rhodium
which have been reported are listed in Table VII. As may or platinum in causing rearrangements during regular
be gathered from the table, virtually all reported work has catalytic hydrogenation of substituted cyclohexenes. l 8
been done with palladium. Under standardized conditions A great deal of emphasis was placed on the prepara-
when palladium is effective, neither platinum nor rhodium tion of the catalyst in early work, but according to the re-
catalysts work, at least at temperatures below 200”. A cent literature, the commercially available catalysts are
more systematic study would be desirable, however, be- perfectly a d e q ~ a t e . ’Palladium
~ is the catalyst of choice
fore this assertion is finalized. for most catalytic transfer hydrogenations.
Recently catalysts used for homogeneous hydrogena-
tion have been used for transfer hydrogenation. These in- E. Other Variables
clude the ruthenium complex R U C I ~ ( P ~ ~ P )the ~ , ’iridium
’
complexes HlrC12(Me2S0)3,1 ’ O.’
3 1 3 Ir(CO)Br(PhSP)z,l3 As is frequently the case with heterogeneous reac-
the rhodium complex RhCI(Ph3P)3,13 and the platinum tions, mechanical agitation is very important. Linstead
+
complex P t C l ~ ( P h 3 A s ) ~ SnC12.H~0.~ In the latter case, has shown that free ebullition is actually rate determining
it is not clear whether the tin or the platinum is the effec- for the catalytic dehydrogenation of tetralols and tetral-
tive catalyst. ones to naphthols.55 Here product distribution, Le., the
Raney nickel occupies a somewhat ambiguous place ratio of naphthalenes to naphthols produced, was deter-
among the catalysts for transfer hydrogenation because mined by temperature. As most catalytic transfer hydro-
of the demonstrated fact that the catalyst contains 40- genations are carried out at reflux, this condition for opti-
110 ml/g of adsorbed hydrogen formed during generation mum reaction is met. Nevertheless, the technique de-
of the ~ a t a l y s t . ~Hence
‘ assertions that reduction with vised by Linstead of carrying out the reaction at lower
Raney nickel is due to hydrogen transfer from a donor temperatures by using a partial vacuum deserves consid-
have been q ~ e s t i o n e d .There ~~ is also evidence that eration when greater selectivity is desired. Alternatively a
some hydrogen is removed from hydroxylic solvents and solvent may be used.
Atkins, et a/., have shown that hydrogen transfer from al-
cohols to ethylene is possible with Raney nickel.54 I t is I 11. Applicability
also clear that Raney nickel plays only a catalytic and
We have chosen to present typical applications of
not a donor role in the oxidation/hydrogen transfer of
transfer hydrogenation with various functional groups and
cholesterol to c h o l e ~ t e n o n e . Again~~ further work is
then to devote a special section to applications with a
needed to determine if the catalyst-bound hydrogen, pos-
more general synthetic interest.
sibly nickel hydride, plays a major role in the quantitative
reduction of multiple bonds, or whether it serves mainly
to “activate” the catalyst.
A. Reduction of Multiple Bonds
For a comparison of the effectiveness of various cata- 1 . Olefins
lysts, see the results presented by Braude, et in A number of different olefins have been reduced by
Table V I I I . Clearly palladium catalysts are the most ef- catalytic transfer hydrogenation. These are listed in Table
fective. With other donors, especially hydrazine, Pt/C
I X which indicates that a considerable variety of olefinic
and Raney nickel seem to work equally well.’ I t is inter-
compounds has been hydrogenated in good to excellent
esting to note that nickel catalysts effect the dispropor- yields by transfer hydrogenation. Nitriles are usually com-
tionation of cyclohexene under very mild conditions. Thus
pletely reduced to methyl groups along with the double
a nickel/kieselguhr catalyst converts cyclohexene quan-
bond. Halogen is generally removed, including halide
titatively at 74” to benzene and cyclohexane in 15 sec.’
bound to an aromatic ring. This will be discussed further
Nonetheless the catalyst is ineffective in hydrogen trans-
in section 111.8.2.
fer to an acceptor other than cyclohexene.
In another system, with limonene as donor and cin-
namic acid as acceptor, platinum and rhodium catalysts
2. Acetylenes
were also found i n e f f e ~ t i v e . ’ ~ In contrast to the extensive work done with olefins,
The exceptional role of palladium in hydrogen transfer only very limited data are available for acetylenes, as
reactions appears to be due, at least in part, to its gener- shown in Table X. Nevertheless, it appears that it is pos-
al mobilizing action for hydrogen-carbon bonds. For in- sible to control the addition so that the intermediate ene
Catalytic Transfer Hydrogenation Chemical Reviews, 1974, Vol. 74, No. 5 571
-
RCN RCH,NH2 The details are given in section I I I .D.
Pd C
RCHZNH, + RCH-NH RCH-NH, DHJ- 2. Halides
I
NHCH,R Halogen in organic compounds is frequently removed
RCH=NCH,R + NH3 under conditions of catalytic transfer hydrogenation. In
addition to the instances cited in Tables I X and XII, the
OH2 cases shown in Table XV have been reported.
- -
RCH=NCH,R (RCH,),NH
From this table it is indicated that chlorine and bro-
Pd C mine bound to an aromatic ring can be removed in good
R C H G N H + (RCH,),NH RCH-NH, yield. One would assume that the same applies to iodine,
I DH2
although no examples were reported. Fluorine, on the
N(cH,R), other hand, is inert. An isolated example of the reduction
(RCH,),N + NH3 of an acid chloride (benzoyl chloride) gave only a mini-
mal yield of benzaldehyde.
5. imines, Hydroxylamines, Hydrazones
3. Allylic and Benzylic Functional Groups
The few reported examples of a carbon-nitrogen dou-
ble bond reduction are listed in Table XIII. Apparently Because of the enhanced reactivity of allylic and ben-
only relatively stable systems were studied, and the gen- zylic compounds, it is to be expected that functional
eral applicability is not clear. As in the case of the ni- groups bound to these systems would hydrogenolyze
triles, the reaction does not stop at intermediate reduc- rather easily as in conventional hydrogenation. This turns
tion stages, but proceeds directly to the corresponding out to be the case with catalytic transfer hydrogenation
alkane, as in conventional hydrogenolysis of benzylic as well. Table XVI gives examples of such reactions. Al-
amines. though the reported examples are not numerous, it is
572 Chemical Reviews, 1974, Vol. 74, No. 5 G. Brieger and T. J. Nestrick
Ketones
Cyclohexanone 3 C Cyclohexanol (97) 10
Mesityl oxide 5 G (C H3)& H C HaCOCH3 (90) 30
PhCH=CHCOCH3 5 G PhCHaCHaCOCHZ (70-100) 14
6 I PhCH2CH2COOCHj (94) 12
6 E PhCHaCHaCOCHa (76) 12
PhCH=CHCOP h 6 I PhCHaCHaCOPh (98) 12
3 C P hCHJCHaC0P h (95) 11
5 G P h CHaC HaCOP h (70-100) 14
3,4-(CHaCHzO)PhCI=CHCOCH3 5 G 3,4-(CH3CHZO)aPhCHiCHICOCH3 (70-100) 14
p.CI P hC H=C HCO P h 5 F P hCHiCHiC0 Ph (d)' 14
Catalytic Transfer Hydrogenation Chemical Reviews, 1974, Vol. 74, No. 5 573
TABLE I X (Continued)
Acceptor Catalysta Donorb Product (yield, %) Ref
p-CHaPhCH=CHCOPh-p-OCHa 4 D p-CHiOPhCH&HzCOPh.p-OCH, (80) 40
5 G p.C H,O P hCH& HzCOP h-p-OCH, (70-100) 14
p-CHaOPhCH=CHCOPh-3,4-(CH3CH20)2 5 F P-CH?OP~CH~CH~COP~-~,~-(O (70-100)
C H ~ C H ~ ) ~ 14
PhCH=CHCOC(CH,), ' 6 I PhCH2CHzCOC(CH,)? (89) 12
3 C PhCHzCH2COC(CHa)?(90) 11
P hCH=CHC H=CH COP h 5 F PhCH&HzCHzCHzCOPh (70-100) 14
3 C P hC H2CHzCHzCHzCOP h (90) 11
P hCH=CH CH=CH CO P h.p.OCH3 5 F P hCHiCH2C H& HZCOP h-p-OCHa (70-100) 14
(PhCH=CH)zCO 3 C (PhCHzCH2)zCO (65) 11
5 F (PhCHz)zCO (4 14
lsophorone 6 I 3,3,5-Trirnethylcyclohexanone (41) 12
Pulegone 1 e Menthone (51) 16
C holestenone 4 f Dihydrocholesterol (10) 40
17~~-Acetoxy-6-methylenepregn-4-ene-3,20-dione 5 A 17~~~Acetoxy.6~~methylpregn~4~ene-3,20dione (?) 29
21-Acetoxy-6-methylenepregn~4-ene-3,20-dione 5 A 21-Acetoxy-6~methylpregn-4-ene-3,20~d1one (1) 29
Aldehydes
Crotonalde hyde 3 C Butyraldehyde (40) 10
Cinnamaldehyde 3 C PhCHZCHzCHO (0-1) 10
P h C H=C(C H3)C H 0 6 I P hC H2C H (C H3)CH 0 (61) 12
17~Acetoxy-6-formyI~3-methoxypregna-3,5-dien~
20-one 5 A 17~~Acetoxy-6~-methylpregn-4-ene.3,20-dione
(?)r 29
5
21-Acetoxy-6~formyl-3-methoxypregna-3,5-dien~2O~one A 21-Acetoxy-6~-methylpregn-4-ene-3,2O~dione
(?)c 29
21-Acetoxy-6-formyl-17-hyd roxy-3-rnethoxypregna-
3,5-d ie ne-11,20.d ione 5 A 6-~0Methylcortisoneacetate (80) 29
Esters
PhCH=CHCOO R A, F PhCHzCHzCOOR (100) 31
(R = CzHj, CdHe, C~HSCHZ)
m-CIPhCH=CHCOOCH3 G PhCHzCHzCOOCHs (90)' 14
Methyl linoleate 9 Monoene ester (51) 9
Nitriles
PhCH=CPhCN 5 H PhCHZCH PhCHa (70-80)' 8
3,4-(CH,O)zPhCH=CHCN 5 H ~ , ~ - P ~ ( C H ~ O ) ~ P ~ C H(70-80)'
ZCH~CH~ 8
p.CH30PhCH=C(p-CHaPh)CN 5 H p-CHiPhCH&H(p-CHaPh)CHz (70-80)c 8
p-CHaPhCH=CPhCN 5 H p-CH?P hC H2C H P hCHi (70-80)' 8
3,4-Methylenedioxy-PhCH=CPhCN 5 H 3,4-Methylenedio~y PhCH~CHPhCH~ (70-80)< 8
P hCH=CHC H=CP hC N 5 H P hCHZCH2CH F H P h CHi (70-80)' 8
PhCH=C(COOCH2CH,)CN 5 H PhCH&H(COOCHzCHa)CH, (81)' 45
PhCH=C(COOCH(CH,)2)CN 5 H PhCHzCH(COOCH(CH1)z)CHa (70)' 45
p.CH,PhCH=C(COOCH2CH,)CN 5 H p.C HT P hCH& H (COOC HzC H,)C H? (63)' 45
~,~.(CH~O)ZP~CH=C(COOCH~CH~)CN 5 H ~ - ~ . ( C H ~ ) ~ P ~ C H ~ C H ~ ( C O O C H (0)
ZCH)CH~ 45
Ph(CHa)C=C(COOCHzCH,)CN 5 H Ph(CH,)CHCH(COOCH?CH,)CH, (59)' 45
Ph(C HaCHz)C=C(COOCH&H3)C N 5 H Ph(CH&H2)CHCH(COOCH&H?)CH, (16)' 45
Miscellaneous Cornpou n d s
Maleic anhydride 5 F Succinic anhydride ( d ) 14
Coumarin 5 G Dihydrocou rnarin ( d ) 14
Barbituric acids 5 F, G,H Corresponding saturated barbituric acids ( d ) 14
Ri Rz Ri Rz
allyl allyl allyl isopropyl
allyl phenyl allyl ethyl
1-cyclohexenyl ethyl
Catalysts: 1, Pd black; 2, RhCh(Ph3P) ; 3, IrCls(Me2SO)a;4, Raney nickel; 5, Pd/C; 6, R U C I ~ ( P ~ ~7,P PtCh(Ph3As)?
)~; SnC12. *Donors: A, cyclo- +
hexene; B, HCOOH/HCOOLi; C, isopropyl alcohol; D, diethylcarbinol; E, tetralin; F, wphellandrene; G, limonene; H,AI-p-rnenthene; I, PhCH?OH.
Concurrent hydrogenolysis. Specific yields not indicated, but approaching quantitative.'* Pulegone (disproport.). Cyclohexanol. v Meth-
anol.
the course of the reaction is more complex as indicated More significant cases of selectivity were encountered
in section 111.8.1. in the steroid series. Here various steroid ethers of the
general type represented in eq 8 were selectively re-
C. Structural Selectivity
The following general comments can be made regard-
ing selectivity. Carbonyl groups are generally not at-
tacked under the usual conditions with Pd/C. Therefore,
ketones, acids, esters, and amides are not changed, as 5% Pd’C
may be seen from Table X I V . Aldehyde groups are cyclohexene
CGHSCHCN
I
-Pd C
C,H,CH,CN (ca. 70%) (7)
ration has been reported as in eq 9.’’
An example of selectivity in the terpene series is the
disproportionation of d-limonene to give A’-p-menthene,
a process which occurs rapidly before any appreciable
OCOC,H,
transfer hydrogenation takes place (eq 10).
without reducing the nitrile.58 Nitro groups are also more Another type of selectivity is found in the reduction of
easily reduced than nitriles (Table X I V ) . polynitrobenzenes. With transfer hydrogenation, only one
Chemical Reviews, 1974, Vol. 74, No. 5 575
Catalytic Transfer Hydrogenation
TABLE XIII. Catalytic Transfer Reduction of C=N nation. This process has been used, for instance, for the
Compounds (Pd/C Catalyst) synthesis of heterocyclic compounds from tne appropri-
ate nitro compounds, as shown in eq 11.,'
Acceptor Donor Product (yield) Ref
NH,(CH,),NH,
Raney nickel
80% n N'
H
+ "3 (12)
..
H
under the appropriate conditions, to synthesize secondary
amines according to e q 14.49 The mechanism is probably
2RCHpNHp -
Raney nickel
(RCH,),NH
70-90%
+ NH, (14)
OCOC,H,
I
Pd/C Cyclohexene 28
CH2R
CH,O 4
R = -N(CH&
CH2R
-'N(CH& -N(CH&
170-Acetoxy-6-hydroxymethyl.3-methoxy.
Raney nickel
Pd/C
Methanol
pH 7-7.5
Cyclohexene
CH30
(75)
17~-Acetoxy~6-methyI-3-methoxy-
28
29
androstane-3,5-diend20-one androstane-3,5-dien-20.one (?)
Benzoin Raney nickel Cyclohexanol Bibenzyl (58) 40
HO HO
HPd H H H
(1 9)
H H
CH2=CH, + CHZ-CHZD CHZ-CH, + CHZECHD anisms which have been proposed to account for the
t I I t isomerization of olefins under the influence of palladium
§ § § § catalyst^,^^-^^ all of which have in common the inter-
(27) mediacy of palladium hydride, H-complexed and a-bond-
ed palladium, and equilibration between these two forms,
CH,-CH2D + D A DCH,-CH,D + 28 (28) such as the mechanism suggested for the scrambling of
I I deuterium label in 3,3-dideuteriobutene-l 6 7 (eq 35 and
8 § 36).
CH,-CH,D + D, + DCH,-CH,D + D (29)
I I CH,=CHCD,CH, * CH,=CHCD,CH,
PdO
t
§ §
2CH,-CH,D
I
- CH,-CH,D + CH,=CHD
t
+ § (30)
PdD
CH,-CHCD,CH, (35)
I 1
d § Pd D
-
be seen.
I C6H&I.CC&/, + HlrCI,(Me,SO),
I n a second step the palladium hydride (still consid-
/C6H5
ered a part of the catalyst and not in solution, of course) as-stilbene (37)
adds to the acceptor as in eq 32. This is followed by a bi-
'IrCI,(Me,SO), 9ooo
C=C
acceptor
+ PdH - c-cI I (32) The second stereochemical aspect, namely the stereo-
chemistry of reduction at a saturated Pd-C bond (hydro-
Pd H genolysis), has been explored with optically active ben-
molecular reaction of the hydride with a donor-palladium zylic halides as shown in eq 38. The reaction is highly
x-allyl complex to give the reduced acceptor and the
dehydrogenated donor (eq 33).
C-C + C-C-C-CH
I I <-.
' 4 ' I I
Pd H Pd COOR COOH
C-C + C=C-C=C + 2Pd (33) stereospecific and leads to i n ~ e r s i o n . ~Intermediate
' for-
I t
H H
mation of a Pd-C bond (with retention) is proposed. So
far no results are available for catalytic transfer hydroge-
Alternatively the x-allyl palladium intermediate can dis- nation.
proportionate with itself, as in eq 34, giving back either We may summarize the mechanistic considerations by
the original or isomerized donor plus dehydrogenated stating that little work has been done in this area, and
donor. This scheme is essentially an adaptation of mech- that those results which are available are not inconsistent
580 Chemical Reviews, 1 9 7 4 , Vol. 74, No. 5 G. Brieger and T. J. Nestrick
with mechanisms proposed for regular catalytic hydroge- (8) K. Kindler and K. Luhrs, Chem. Ber., 99, 227 (1966).
nation. Of particular interest, however, is the role of the (9) J. C. Bailar, Jr., and H. Hatani, J . Amer. Chem. SOC.. 89, 1592
(1967).
donor in such reactions, and this remains to be explored. (10) M. Gullotti, R. Ugo, and S. Colonna, J. Chem. SOC.C, 2652 (1971).
(11) J. Trocha-Grimshaw and H. 8. Henbest. Chem. Commun., 544
(1967).
V . Summary and Prospects (12) Y. Sasson and J. Blum, Tetrahedron Lett.. 2167 (1971).
(13) M. E. Volpin, V. P. Kukolev, V. 0. Chernyshev, and I . S. Kolomni-
We have endeavored to show that an interesting alter- kov, Tetrahedron Left.. 4435 (1971).
native to conventional catalytic hydrogenation exists in (14) K. Kindler and K. Luhrs, Justus Liebigs Ann. Chem., 685, 36
(1965).
catalytic transfer hydrogenation with an organic molecule (15) R. P. Linstead, A. F. Millidge, S. L. S. Thomas, and A. L. Walpole,
as hydrogen donor. This reaction, using predominantly J. Chem. SOC., 1146 (1937).
(16) R. P. Linstead, K. 0. A. Michaelis, and S. L. S. Thomas, J. Chem.
palladium, but occasionally also Raney nickel, or soluble SOC., 1139 (1940).
transition metal catalysts, permits the reduction of a wide S. Siegel and G. V. Smith, J. Amer. Chem. SOC.,82, 6087 (1960).
variety of olefins, nitriles, nitro compounds, and other ni- A. S. Hussey, T. A. Schenach, and R. H. Baker, J. Org. Chem.. 33,
3258 (1968).
trogen-containing unsaturated functional groups, as well S.Akabori and K. Saito, Chem. Ber., 63, 2245 (1930).
as hydrogenolysis of benzylic and allylic functional R. C. Elderfield and A. Maggiolo. J. Amer. Chem. Soc.. 71, 1906
(1949).
groups and the replacement of aromatic halogen. The W. Doering and S. J. Rhoads, J. Amer. Chem. SOC., 75, 4738
donors are readily available organic compounds such as (1953).
cyclohexene and alcohols. The yields are in most cases J. Heer and K. Miescher, HeIV. Chim. Acta, 31, 1289 (1948).
H. Atkins, L. M. Richards, and J. W. Davis, J. Amer. Chem. SOC.,
excellent and fully comparable to those of normal catalyt- 63, 1320 (1941).
ic hydrogenation. The reaction is somewhat more selec- (24) R. P. Linstead and S. L. S. Thomas, J. Chem. SOC.,1127 (1940).
tive than regular hydrogenation and in special cases, (25) A. Giaffe and R. Pallaud, C. R. Acad. Sci., 259, 4722 (1964).
(26) A. Giaffe and A. Plotiau. C. R. Acad. Sci., 261, 164 (1965).
such as the reduction of polyunsaturated steroids, has (27) R. T. Coutts and J. B. Edwards, Can. J. Chem.. 44, 2009 (1966).
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