Carbonylation (hydroformylation and hydrocarbalkoxylation) and enantioselective carbonylation of some methacrylic acid derivatives

Consiglio, Giambattista; Kollár, László; Kölliker, Robert

doi:10.1016/0022-328x(90)85478-h

Cited by 50 publications

(13 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Mais recentemente, o metacrilato de metila foi submetido à hidroformilação assimétrica na presença de complexos de Pt(II) com difosfinas quirais e SnCl 2 7,78,79 . Utilizando-se [(-)-BPPM] PtCl 2 /SnCl 2 como precursor catalítico, este éster fornece o aldeído-éster menos ramificado, na configuração (R) com 60% de excesso enantiomérico 7 (esquema 16), que constitui uma unidade isoprênica funcionalizada, utilizável na síntese de moléculas importantes, tal como o α-tocoferol (cadeia lateral), em substituição a intermediários quirais derivados de compostos terpênicos naturais 80 .…”

Section: Fármacos Diversosunclassified

Contribuições recentes da reação de hidroformilação na síntese de produtos farmacêuticos: parte II

Botteghi¹,

Marchetti²,

Ponte³

1997

Quím. Nova

View full text Add to dashboard Cite

Preto-USP-Via do Café s/n-14040-903-Ribeirão Preto-SP Recebido em 19/12/95; aceito em 16/10/96 CURRENT IMPROVEMENT TO THE SYNTHESIS OF PHARMACEUTICALS BY HYDROFOR-MYLATION REACTION. PART II. The hydroformylation reaction represents one of the most important C1-chemistry area in the chemical industry. This catalytic process, which has been developed up to now mainly to the production of commodities chemicals, has shown a remarkable potential for the preparation of several categories of specialty chemicals and in particular pharmaceutical compounds. Arylpropanoic acids, various amines containing aryl groups, and intermediates for the preparation of vitamins, carbocyclic and heterocyclic compounds and many other classes of organic molecules endowed with pharmacological activity are currently accessible in good-to-high yields through hydroformylation of selected olefinic substrates. The asymmetric hydroformylation is going to reach the stage of maturity and hence to contribute in solving many troublesome synthetic problems connected with the preparation of pharmacologically active compounds with very high enantiomeric purity. The present survey emphasizes the usefulness of synthesis gas as a starting material in fine chemistry, which is expected to be important for industry.

show abstract

Section: Fármacos Diversosunclassified

Contribuições recentes da reação de hidroformilação na síntese de produtos farmacêuticos: parte II

Botteghi¹,

Marchetti²,

Ponte³

1997

Quím. Nova

View full text Add to dashboard Cite

show abstract

“…31). (28) The same class of products was formed by oxidative carbonylation of 1substituted prop-2-ynylamines. (29) The intramolecular cyclocarbonylation of 3-iodo-2-heptylamines in the presence of PdCl 2 (PPh 3 ) 2 resulted in the formation of lactams in good yields.…”

Section: Catalytic Synthesis Of Five- Six- and Seven-membered Ringsmentioning

confidence: 96%

The Application of Transition Metal Catalysis for Selective Cyclocarbonylation Reactions. Synthesis of Lactones and Lactams

Ali¹,

Alper²

2000

Synlett

100

View full text Add to dashboard Cite

A variety of 5-, 6-, and 7-membered ring lactones and lactams have become available via carbonylative cyclization reactions catalyzed by different transition metal complexes. Palladium and rhodium complexes are the most widely used catalysts for the cyclization reactions. Furanones can be synthesized either by the catalytic intermolecular cyclocarbonylation of iodoarenes with alkynes or alkynols, or by intramolecular cyclocarbonylation of alkynols. g-Butyrolactones are mainly prepared by the intramolecular cyclocarbonylation of allyl alcohol derivatives catalyzed by palladium(0) complexes and 1,4-bis(diphenylphosphino)butane (dppb). The replacement of dppb by a chiral ligand leads to the formation of optically active γ-butyrolactones. Furthermore, 5-, 6-, and 7-membered ring bicyclic and polycyclic lactones and lactams are obtained by the Pd(II) catalyzed intramolecular cyclocarbonylation of 2-allylphenol and 2-allylaniline derivatives in the presence of syngas. The regiochemical control of the reaction depends on the choice of solvent, the nature of the metal and added ligand, and the relative pressures of the gases (CO and H 2 ). Lactones 2.3Synthesis of Five-, Six-, and Seven-Membered Ring bicyclic and polycyclic Lactones 3Catalytic Synthesis of Five-, Six-, and Seven-Membered Rings Lactams 4Conclusion

show abstract

“…The substrate scope for the hydroformylation of dialkyl acrylamides 1x 1-4 has so far been limited to methacrylamide, acrylamide or N-benzyl acrylamide, with low enantioselective induction (20-50% ees) [113,114]. However, the use of a bis-diazaphospholane ligand (66a) in the Rh-catalyzed asymmetric hydroformylation of N,N-dialkyl acrylamides was recently described, achieving nearly total regioselectivity and ees up to 82% (Scheme 26) [115].…”

Section: Other Substratesmentioning

confidence: 99%

Asymmetric Hydroformylation

Perandones

Godard

Claver

2013

Topics in Current Chemistry

View full text Add to dashboard Cite

Rhodium is currently the metal of choice to achieve high enantioselectivities in the hydroformylation of a relatively wide variety of alkene substrates. The elucidation of the different steps of the catalytic cycle and the characterization of the resting state, together with the discovery of several types of ligands that are able to provide high enantioselectivities, have made the rhodium-catalyzed hydroformylation a synthetically useful tool. For years, ligands containing phosphite moieties such as diphosphites and phosphine-phosphites were considered the most successful ligands to achieve high enantioselectivities for classical substrates such as styrene and vinyl acetate. In fact, the phosphite-phosphine BINAPHOS (43) and its derivatives are still today the most successful ligands in terms of selectivity and scope. For more substituted substrates, general trends can be extracted. However, recent studies showed that these general trends can be sometimes reversed by the use of the appropriate catalyst and choice of reaction conditions, clearly showing that these trends are only indicative and that there are still many challenges to be tackled in this area.

show abstract

Carbonylation (hydroformylation and hydrocarbalkoxylation) and enantioselective carbonylation of some methacrylic acid derivatives

Cited by 50 publications

References 19 publications

Contribuições recentes da reação de hidroformilação na síntese de produtos farmacêuticos: parte II

Contribuições recentes da reação de hidroformilação na síntese de produtos farmacêuticos: parte II

The Application of Transition Metal Catalysis for Selective Cyclocarbonylation Reactions. Synthesis of Lactones and Lactams

Asymmetric Hydroformylation

Contact Info

Product

Resources

About