Rhodium catalyzed hydrogenation alkenes

Rhodium species in oxidation states I and III are involved in the process. Rhodium-catalyzed hydrogenations generally involve oxidative addition reactions, followed by the reverse process of reductive elimination in the final step. Another common elimination process is the so-called (l-elimination, which accounts for the frequent side reaction of isomerization of alkenes, according to Eq. (1) ... 

It thus came as a surprise that in the year 2000, three groups independently reported the use of three new classes of monodentate ligands (Scheme 28.2) [12], The ligands induced remarkably high enantioselectivities, comparable to those obtained using the best bidentate phosphines, in the rhodium-catalyzed enantioselective alkene hydrogenation. All three being based on a BINOL backbone, and devoid of chirality on phosphorus, these monophosphonites [13], monophosphites [14] and monophosphoramidites [15] are very easy to prepare and are equipped with a variable alkyl, alkoxy, or amine functionality, respectively. 

Wittig yhdes have been shown to be compatible with hydroformylation conditions, and may thus be used in a domino reaction sequence such as from 16a to 38 (Scheme 5.15) [20]. When an a-unsubstituted ylide is employed, the resulting alkene undergoes in-situ rhodium-catalyzed hydrogenation in a triple tandem reaction to convert 10 a to 39. Several other examples were reported establishing the generality of this domino reaction sequence. 

The less-hindered phenyl-substituted monodentate phosphetanes 79, however, give stable rhodium complexes and moderate to high enantioselectivities (up to 86% ee) in rhodium-catalyzed hydrogenation of functionalized alkenes <2001S2095>. 

The rhodium-catalyzed hydrogenation of alkenes (see Hydrogenation Isomerization of Alkenes) has also... 

The influence of the electronic properties of the alkene on the insertion rate has been evaluated in the kinetic study of the reaction of a Rh(III) dihydrido complex and / ara-substituted styrenes (Scheme 6.8) [45]. The process is part of the proposed mechanism for the rhodium catalyzed hydrogenation of alkenes. Under pseudo-first order conditions (excess of PR3 and alkene) in benzene the rate law is -d[RhH2Cl(PR3)]/dt = A obs[RhH2Cl(PR3)] with Us = i k[alkene]/ [PR3] + fir [alkene]. The values of K and k determined for different para-substituted styrenes show that more electron withdrawing substituents in the substituted styrene ring increase the value of K (better alkene coordination), but decrease k (slower insertion). These opposite trends tend to cancel each other and the overall rates of the process vary little for different styrenes. K values are in the range... 

Halpern J, Okamoto T and Zakhariev A 1976 Mechanism of the chlorotris(triphenylphosphine)rhodium(l)-catalyzed hydrogenation of alkenes J. Mol. Catal. 2 65-9... 

In 1968,Horner et al. [22] and Knowles and Sabacky [23] independently demonstrated that low but definite enantiomeric excesses (up to 15% ee) were produced in the rhodium-catalyzed asymmetric hydrogenation of simple alkenes using methylpropylphenylphosphine 7 as chiral ligand (Scheme 1). 

Another important reaction principle in modem organic synthesis is carbon-hydrogen bond activation [159]. Bergman, Ellman, and coworkers have introduced a protocol that allows otherwise extremely sluggish inter- and intramolecular rhodium-catalyzed C-H bond activation to occur efficiently under microwave heating conditions. In their investigations, these authors found that heating of alkene-tethered benzimidazoles in a mixture of 1,2-dichlorobenzene and acetone in the presence of di-//-... 

In 1968, Knowles et al. [1] and Horner et al. [2] independently reported the use of a chiral, enantiomerically enriched, monodentate phosphine ligand in the rhodium-catalyzed homogeneous hydrogenation of a prochiral alkene (Scheme 28.1). Although enantioselectivities were low, this demonstrated the transformation of Wilkinson s catalyst, Rh(PPh3)3Cl [3] into an enantioselective homogeneous hydrogenation catalyst [4]. 

Scheme 10.8 outlines the application of rhodium-catalyzed allyhc amination to the preparation of (il)-homophenylalanine (J )-38, a component of numerous biologically active agents [36]. The enantiospecific rhodium-catalyzed allylic amination of (l )-35 with the lithium anion of N-benzyl-2-nitrobenzenesulfonamide furmshed aUylamine (R)-36 in 87% yield (2° 1° = 55 1 >99% cee) [37]. The N-2-nitrobenzenesulfonamide was employed to facilitate its removal under mild reaction conditions. Hence, oxidative cleavage of the alkene (R)-36 followed by deprotection furnished the amino ester R)-37 [37, 38]. Hydrogenation of the hydrochloride salt of (l )-37 followed by acid-catalyzed hydrolysis of the ester afforded (i )-homophenylalanine (R)-3S in 97% overall yield. 

Rhodium-Catalyzed Asymmetric Hydrogenation of Functionalized Alkenes... 

A multistep pathway analogous to the mechanism of alkene hydrogenation has been shown to be operative in the rhodium-catalyzed hydroboration of alkenes.363 Deuterium labeling studies furnished evidence that the reversibility of the elementary steps is strongly substrate-dependent. The key step is hydride rather than boron migration to the rhodium-bound alkene. 

Rhodium(II) acetate catalyzes C—H insertion, olefin addition, heteroatom-H insertion, and ylide formation of a-diazocarbonyls via a rhodium carbenoid species (144—147). Intramolecular cyclopentane formation via C—H insertion occurs with retention of stereochemistry (143). Chiral rhodium (TT) carboxamides catalyze enantioselective cyclopropanation and intramolecular C—N insertions of CC-diazoketones (148). Other reactions catalyzed by rhodium complexes include double-bond migration (140), hydrogenation of aromatic aldehydes and ketones to hydrocarbons (150), homologation of esters (151), carbonylation of formaldehyde (152) and amines (140), reductive carbonylation of dimethyl ether or methyl acetate to 1,1-diacetoxy ethane (153), decarbonylation of aldehydes (140), water gas shift reaction (69,154), C—C skeletal rearrangements (132,140), oxidation of olefins to ketones (155) and aldehydes (156), and oxidation of substituted anthracenes to anthraquinones (157). Rhodium-catalyzed hydrosilation of olefins, alkynes, carbonyls, alcohols, and imines is facile and may also be accomplished enantioselectively (140). Rhodium complexes are moderately active alkene and alkyne polymerization catalysts (140). In some cases polymer-supported versions of homogeneous rhodium catalysts have improved activity, compared to their homogenous counterparts. This is the case for the conversion of alkenes direcdy to alcohols under oxo conditions by rhodium—amine polymer catalysts... 

Table 6, entry 48) whereas alkene isomerization is very slow [52]. Photochemistry is also used in the rhodium-catalyzed alkylborylation of alkanes in which boroalk-anes (Table4, entry 49) are obtained [53], An example of a gas-phase reaction is the photochemical mercury-catalyzed hydroxymethylation of cyclohexane to hydroxymethylenecyclohexane (Table 6, entry 50). This reaction is an example of the abstraction of a hydrogen atom from an alkane by an excited metal atom [54]. 

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