Stereoselective syntheses. VIII. Retentive nucleophilic displacements of .alpha.-substituted alkylferrocenes

Gokel, George W.; Marquarding, Dieter; Ugi, Ivar

doi:10.1021/jo00985a002

Cited by 280 publications

(89 citation statements)

References 14 publications

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“…Another remarkable feature is that nucleophilic displacement reactions at the α-position proceed with complete retention of configuration [30]. This is due to the stabilization of the carbenium ion via an overlap with an iron lone pair (13A).…”

Section: Synthetic Routes Towards Chiral 12-disubstituted Pn-ferrocmentioning

confidence: 99%

Ferrocene-derived P,N ligands: synthesis and application in enantioselective catalysis

Noël¹,

Eycken²

2013

Green Processing and Synthesis

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Due to their unique steric and electronic properties, air-stability and modular structure, chiral hybrid P,N-ferrocenyl ligands play a prominent role in the field of asymmetric catalysis. This report aims to give a concise introduction to the syntheses of chiral hybrid P,N-ferrocenyl ligands and presents an overview of their application in enantioselective catalysis. This review is of special interest to chemists working on ligand design and asymmetric catalysis, as well as to the broader organic and inorganic community.

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Section: Synthetic Routes Towards Chiral 12-disubstituted Pn-ferrocmentioning

confidence: 99%

Ferrocene-derived P,N ligands: synthesis and application in enantioselective catalysis

Noël¹,

Eycken²

2013

Green Processing and Synthesis

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“…A crown ether containing a ferrocene unit, pentaoxa [13]ferrocenophane, 8, was reported by Saji and Kinoshita. 6 Electrochemical studies showed an abrupt decrease in its cation binding constants by electrochemical oxidation of ferrocene.…”

Section: Choice Of Ferrocene As the Redox Switchmentioning

confidence: 89%

“…Compounds 13-18 were prepared by a Williamson reaction 13 that takes advantage of the extraordinary stability of the ␣-ferrocenylmethyl carbocation.…”

Section: Compound Synthesesmentioning

confidence: 99%

Redox-Switched Amphiphiles: Oxidized Ferrocene Derivatives Form Stable Vesicles When Either One or Two Alkyl Tails Are Present

Wang

Gokel

1997

J. Phys. Org. Chem.

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Thirty ferrocene derivatives were prepared and their ability to form vesicles in aqueous solution when oxidized was assessed. The compounds included alkyl ferrocenylmethyl ether derivatives of the form C 10 H 9 FeCH 2 OR in which R = octyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosanyl. One single-tailed amine derivative, C 10 H 9 FeCH 2 NR 2 , R = octadecyl, was studied. Alkylferrocene derivatives had the form C 10 H 9 FeR in which R = butyl, decyl, tetradecyl, hexadecyl, octadecyl, eicosanyl and docosanyl. Sixteen symmetrical 1,1Ј-disubstituted ferrocenes were also studied. Three ethers were of the form C 10 H 8 Fe-1,1Ј-(CH 2 OR), 2 , R = tetradecyl, hexadecyl and octadecyl. Four corresponding dialkyl derivatives of the form C 10 H 8 Fe-1,1Ј-R 2 , R = decyl, tetradecyl, hexadecyl and octadecyl, were assessed. Finally, a range of 1,1Ј-disubstituted ferrocene derivatives were analyzed. These all had the form C 10 H 8 Fe-1,1Ј-(COR) 2 , for which R has the following identities: octyl, tridecyl, pentadecyl and heptadecyl (ketones); heptadecyloxy, 3-cholesteryl and 3-cholestanyl (esters); and two amides, R = NHC 18 H 37 and N(C 18 H 37 ) 2 . The alkyl and ether derivatives could be readily oxidized and formed vesicular aggregates upon sonication. The ketones, esters and amides could be oxidized but the ferricenium derivatives did not form stable aggregates. An interesting observation is that the aggregates formed were vesicular whether the ferrocene derivative had one or two alkyl tails.

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“…In addition, there is a steadily increasing interest in these compounds because of their important role as chiral ligands in homogeneous asymmetric catalysis [3] . Due to nucleophilic substitution reactions, which take place under complete retention of the configuration, a broad variety of ligands can be synthesized based on (1-ferrocenylalkyl)amines [4] . These ferrocenylamines have been conveniently prepared through the diastereoselective ortholithiation of optically active N,N-dimethyl- (1-ferrocenylethyl)amine (e.g.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of (1-Ferrocenylalkyl)amine and 1,1′-Bis(1-aminoalkyl)ferrocene Derivatives

Enders¹,

Lochtman

1998

Eur. J. Org. Chem.

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The aldehydes 1 and 5 were converted to the corresponding SAMP hydrazones 2 and 6, respectively. Subsequent nucleophilic 1,2‐addition of organolithium reagents to the C−N double bonds and cleavage of the N−N hydrazine bond using an excess of BH3·THF afforded (1‐ferrocenylalkyl)amines (N‐protection → 4) and 1,1′‐bis(1‐aminoalkyl)ferrocenes (N‐protection → 8) in good overall yields (32−88%), with very high enantiomeric excesses (ee = 90−98%) and dl/meso ratios of up to 95:5.

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Stereoselective syntheses. VIII. Retentive nucleophilic displacements of .alpha.-substituted alkylferrocenes

Cited by 280 publications

References 14 publications

Ferrocene-derived P,N ligands: synthesis and application in enantioselective catalysis

Ferrocene-derived P,N ligands: synthesis and application in enantioselective catalysis

Redox-Switched Amphiphiles: Oxidized Ferrocene Derivatives Form Stable Vesicles When Either One or Two Alkyl Tails Are Present

Asymmetric Synthesis of (1-Ferrocenylalkyl)amine and 1,1′-Bis(1-aminoalkyl)ferrocene Derivatives

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