Big Chemical Encyclopedia

Chemical substances, components, reactions, process design ...

Articles Figures Tables About

Dienes catalysts, rhodium complexes

The addition of allcenes to alkenes can also be accomplished by bases as well as by the use of catalyst systems consisting of nickel complexes and alkylaluminum compounds (known as Ziegler catalysts), rhodium catalysts, and other transition metal catalysts, including iron. These and similar catalysts also catalyze the 1,4 addition of alkenes to conjugated dienes, for example. [Pg.1020]

The synthesis of cationic rhodium complexes constitutes another important contribution of the late 1960s. The preparation of cationic complexes of formula [Rh(diene)(PR3)2]+ was reported by several laboratories in the period 1968-1970 [17, 18]. Osborn and coworkers made the important discovery that these complexes, when treated with molecular hydrogen, yield [RhH2(PR3)2(S)2]+ (S = sol-vent). These rhodium(III) complexes function as homogeneous hydrogenation catalysts under mild conditions for the reduction of alkenes, dienes, alkynes, and ketones [17, 19]. Related complexes with chiral diphosphines have been very important in modern enantioselective catalytic hydrogenations (see Section 1.1.6). [Pg.10]

This catalyst system was the first to utilize both terminal alkynes and olefins in the intramolecular reaction. Although a mechanistic rationale for the observed stereoselectivity was not offered, the formation of the single stereoisomer 26 may be rationalized through the diastereotopic binding of the rhodium complex to the diene moiety (Scheme 12.3). This facial selective binding of the initial ene-diene would then lead to the formation the metallacycle III, which ultimately isomerizes and reductively eliminates to afford the product [14]. [Pg.244]

NaOH-HiOz) or to carboxylic acids (with w-chloroperbenzoic acid).-190 Double bonds can be hydroborated in the presence of triple bonds if the reagent is 9-BBN.191 On the other hand, dimesitylborane selectively hydroborates triple bonds in the presence of double bonds.192 Furthermore, it is often possible to hydroborate selectively one particular double bond of a nonconjugated diene.191 When the reagent is catecholborane, hydroboration is catalyzed by rhodium complexes, such as Wilkinson s catalyst.194 Enantioselective hydro-boration-oxidation has been achieved by the use of optically active rhodium complexes.195... [Pg.788]

Asymmetric hydrogenation of alkenes is efficiently catalysed by rhodium complexes with chiral diphosphite and diphosphoramidite ligands derived from BINOL or diphenylprolinol. Choice of a proper achiral backbone is crucial.341 Highly enantioselective hydrogenation of A-protected indoles was successfully achieved by use of the rhodium catalyst generated in situ from [Rh(nbd)2]SbF6 (nbd = norborna-2,5-diene)... [Pg.134]

Probably the most important developments in this field over the past 10 years, however, have been in the area of enantioselective see Enantioselectivity) hydroborations using cationic rhodium complexes of the type [Rh(diene)L ]+ (L = chiral ligand). An excellent review on this topic has recently been published. New chiral see Chiral) catalyst systems are typically tested in hydroborations of vinyl arenes. Although catalyzed hydroboration of vinyl arenes can be used as a mild and efficient route to preparing 1-arylethanol... [Pg.1570]

In contrast to olefins, little is known on catalytic hydroboration of conjugated dienes. Suzuki and Miyaura20 described a 1,4-addition of catecholborane to acyclic 1,3-dienes, catalyzed with tetrakis(triphenylphosphine)pa]ladium(0). An interesting Markovnikov type regioselectivity was observed in the enantioselective dihydroboration of (E)-1-phenyl-1,3-butadiene with catecholborane, catalyzed by chiral rhodium complexes.21 However, the scope of these reactions is not well known, and the choice of catalysts is very limited. [Pg.418]

Butadiene Hydrogenation. Rhodium complexes of the type Rh(diene)(dppe)+, where dppe = 1,2-bis(diphenylphosphino)ethane, are catalyst precursors for overall 1,2 and 1,4 addition of hydrogen to 1,3-butadienes. In these reactions the distribution of terminal and internal olefin products is kinetically regulated by the reaction pathways of a common RhH(R)(dppe)+ intermediate (13). Under homogeneous reaction conditions, the thermodynamically more stable internal olefin products (1,4-addition) are favored over the synthetically more useful terminal olefin products (1,2 addition). However, significant increases in the yield of 1,2 addition products can be achieved by intercalation of the catalyst precursor in hectorite. (14)... [Pg.247]

Asymmetric Hydrogenation. Rhodium complexes of the type Rh(diene)(diphos )+, where diphos is a chiral bidentate diphosphine ligand, are catalyst precursors for the asymmetric hydrogenation of certain prochiral olefins (15). Asymmetric hydrogenation of a-acylaminoacrylates, for example, affords chiral amino acid derivatives, some of which have medicinal utility such as L-DOPA. [Pg.247]

Amino-derived BDPP (2,4-bis[diphenylphosphino]pentane) has been used in asymmetric hydrogenation catalysis [15-17] (cf. Sections 6.2 and 6.9). NMR analysis showed that a ten-fold excess of HBF4 is sufficient to protonate reversibly all four amino groups in the [Rh(diene)(BDPP)]BF4 complex. Recycling of the catalyst after enantioselective hydrogenation of dehydroamino acid derivatives in methanol is achieved by acidification with aqueous FIBF4 followed by extraction of the product with Et20. Immobilization of the protonated BDPP rhodium complex on a Nafion support has been studied as well [18]. [Pg.690]

The hydroformylation of conjugated dienes such as 1,3-butadiene, isoprene, and 1,3-pentadiene gives mixtures of regioisomers, isomerized aldehydes, and dialdehydes depending on the conditions and catalysts used. The reaction of 1,3-butadiene provides 1,6-hexanedial and has relevance to nylon produc-The reaction of 1,3-cyclohexadiene catalyzed by a rhodium complex... [Pg.18]


See other pages where Dienes catalysts, rhodium complexes is mentioned: [Pg.121]    [Pg.1016]    [Pg.1037]    [Pg.9]    [Pg.328]    [Pg.115]    [Pg.161]    [Pg.174]    [Pg.362]    [Pg.919]    [Pg.9]    [Pg.28]    [Pg.405]    [Pg.406]    [Pg.468]    [Pg.563]    [Pg.473]    [Pg.15]    [Pg.243]    [Pg.252]    [Pg.35]    [Pg.173]    [Pg.390]    [Pg.432]    [Pg.95]    [Pg.99]    [Pg.189]    [Pg.1135]    [Pg.182]    [Pg.582]    [Pg.50]    [Pg.1082]    [Pg.919]    [Pg.446]    [Pg.255]    [Pg.446]    [Pg.133]    [Pg.134]    [Pg.181]    [Pg.28]   
See also in sourсe #XX -- [ Pg.266 ]

See also in sourсe #XX -- [ Pg.266 ]

See also in sourсe #XX -- [ Pg.6 , Pg.266 ]




SEARCH



1.3- Dienes complexes

Complex diene

Rhodium catalysts catalyst

Rhodium complex catalysts

Rhodium complex catalysts cationic diene complexes

Rhodium complexes diene

© 2024 chempedia.info