Ferrocenyl bis-phosphine ligands bearing sulfinyl, sulfonyl or sulfenyl groups: applications in asymmetric hydrogenation and allylic alkylation reactions

Raghunath, Malati; Gao, Wenliang; Zhang, Xumu

doi:10.1016/j.tetasy.2005.08.036

Cited by 30 publications

(20 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The biferrocenyl diphosphine 86 (Scheme 17) gave a rhodium catalyst for the asymmetric hydrogenation of methyl N-acetyldehydroalanine (93 % ee). [52] Scheme 16. Suzuki or Negishi couplings on a ferrocene sulfoxide.…”

Section: Some Results In Enantioselective Catalysismentioning

confidence: 99%

“…[14,51] The 1,1'-bisphosphines 67 have been prepared by Zhang et al from 1,1'-bis(tert-butylsulfinyl)-phosphinoferrocene, itself prepared by enantioselective oxidation of 1,1'-bis((tert-butylsulfenyl)ferrocene. [52] The monophosphine 68 bearing a sulfenyl group in the ortho-position represents a class of ligands developed by Carretero et al and which gave rise to useful palladium catalysts. [53,54] These compounds were easily obtained from the key sulfoxides 4a and 4b, by ortholithiation, addition of one equiv.…”

Section: Synthesis Of Chiral Ligands For Enantioselective Catalysismentioning

confidence: 99%

See 1 more Smart Citation

Metallocene Sulfoxides as Precursors of Metallocenes with Planar Chirality

Ferber

Kagan

2007

Adv Synth Catal

View full text Add to dashboard Cite

The preparation of metallocene sulfoxides and their ortho-diastereoselective functionalization are described. The applications of enantiopure 1,2-and 1,3-disubstituted metallocenes are reviewed, with special emphasis on the preparation of ligands for asymmetric catalysis. The sulfoxide functionality is a useful, traceless, chiral diastereoselective orthodirecting group, as explained in the article. It allows one to synthesize a wide range of enantiopure metallocenes with planar chirality and predictible configuration. Most of the examples are related to the ferrocene area.

show abstract

Section: Some Results In Enantioselective Catalysismentioning

confidence: 99%

Section: Synthesis Of Chiral Ligands For Enantioselective Catalysismentioning

confidence: 99%

Metallocene Sulfoxides as Precursors of Metallocenes with Planar Chirality

Ferber

Kagan

2007

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

“…Generally, the influence of the base additive in the BSA/base system is difficult to elucidate and it depends on the individual catalytic system [13f]. However, a similar pronounced BSA/activator effect has been observed in the Pd-catalyzed AAA in the presence of C 2 -symmetric ferrocene diphosphine-disulfone [24] as well as with imidate-phosphine ligands [25]. Switching the ligand to tetrahydrodeoxocytisine derived 7, containing additional amino group, dropped the enantioselectivity remarkably.…”

Section: Methodsmentioning

confidence: 92%

Cytisine as a scaffold for ortho-diphenylphosphinobenzenecarboxamide ligands for Pd-catalyzed asymmetric allylic alkylation

Philipova

Stavrakov

Vassilev

et al. 2015

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…Rhodium-Catalyzed Hydrogenation a-(N-acetamido)acrylate in the Presence of Ligand 20 [26] A solution of [Rh-(NBD) 2 SbF 6 ] (2.3 mg, 0.0050 mmol) and ligand 20 (4.4 mg, 0.0055 mmol) in MeOH (5 mL) was stirred in a glove box for 10 min to allow the formation of catalyst. The complex solution (1 mL) was then put in each of the hydrogenation vials.…”

Section: 103mentioning

confidence: 99%

“…The use of planar chirality was also explored by Zhang et al [26] with the application of the bis-sulfone phosphine ligand 20 in Pd-catalyzed allylic alkylations (Scheme 9.5). Different additives were evaluated in the transformation and a dramatic increase in the enantioselectivity was observed by changing the alkali metal ions from Li þ to Cs þ .…”

mentioning

confidence: 99%

Sulfur‐ and Selenium‐Containing Ferrocenyl Ligands

Carretero

Adrio

Rivero

2009

Chiral Ferrocenes in Asymmetric Catalysis

View full text Add to dashboard Cite

Since the synthesis of ppfa (N,N-dimethyl-1-[2-(diphenylphosphino)ferrocenyl]ethylamine), described by Hayashi and Kumada in 1974 [1], there has been a growing interest in chiral bidentate ferrocene ligands. In particular, in the last 15 years an amazing number of ferrocene ligands, frequently combining central and planar chirality and P,P-(e.g., Josiphos, Walphos, BoPhoz, Taniaphos) or P,N-coordination (e.g., ppfa, phosphino ferrocenyl oxazolines, phosphino imine ferrocenes) have been developed, providing high reactivities and enantioselectivities in an ample variety of metal-mediated reactions [2]. However, in spite of the well known ability of thioethers and thiols to coordinate late transition metals, to the best of our knowledge, the first examples of enantiopure ferrocene sulfur ligands in asymmetric catalysis were not reported until 1996, independently, by Togni [3] and Albinati and Pregosin [4]. In both cases this pioneering work involved the use of a 1,2-disubstituted bidentate P,S-ferrocene ligand, derived from ppfa-type ligands, in standard Pd-catalyzed asymmetric allylic alkylations.In very recent years, in parallel with the increasing interest in sulfur ligands in asymmetric catalysis [5], a variety of sulfur-containing ferrocenyl ligands (and some scattered examples of selenium related ligands) have been described by different groups and successfully employed in several asymmetric catalytic processes, although the Pd-catalyzed asymmetric alkylation continues to be the most studied reaction. In agreement with the growing interest in sulfur-containing ferrocene ligands, the first specific review on this topic has been very recently written by Bonini and Ricci [6]. In this chapter we want to give a clear view of the most significant contributions in this recent and promising field, including our own work with chiral planar 2-phosphino 1-sulfenyl ferrocenes (Fesulphos ligands), with especial focus on the results in asymmetric catalysis rather than the synthetic aspects of the preparation of the sulfur-containing ferrocene ligands.

show abstract

Ferrocenyl bis-phosphine ligands bearing sulfinyl, sulfonyl or sulfenyl groups: applications in asymmetric hydrogenation and allylic alkylation reactions

Cited by 30 publications

References 18 publications

Metallocene Sulfoxides as Precursors of Metallocenes with Planar Chirality

Metallocene Sulfoxides as Precursors of Metallocenes with Planar Chirality

Cytisine as a scaffold for ortho-diphenylphosphinobenzenecarboxamide ligands for Pd-catalyzed asymmetric allylic alkylation

Sulfur‐ and Selenium‐Containing Ferrocenyl Ligands

Contact Info

Product

Resources

About