Unexpected acid-catalyzed ferrocenylmethylation of diverse nucleophiles with vinyloxymethylferrocene

Опарина, Л. А.; Artem’ev, Alexander V.; Vysotskaya, O. V.; Тарасова, О. А.; Шагун, В. А.; Bagryanskaya, I. Yu.; Трофимов, Б. А.

doi:10.1016/j.tet.2016.06.012

Cited by 13 publications

(2 citation statements)

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“…All volatiles were removed in vacuo. Purification was realized by column chromatography (silica, 4.5 × 22 cm column size) using hexane for the elution of methylferrocene 7 [85] (50 mg, 0.25 mmol, 3 % based on 1a) and 8, followed by a 1:1 hexane/dichloromethane mixture (v/v) giving bis(ferrocenylmethyl)ether 6a [86] (886 mg, 2.14 mmol, 46 % based on 1a) and 1a (242 mg, 1.12 mmol, 12 % based on 1a). After evaporation of all volatiles in vacuo all compounds were obtained as orange solids.…”

Section: Electrochemistrymentioning

confidence: 99%

(Planar‐Chiral) Ferrocenylmethanols: From Anionic Homo Phospho‐Fries Rearrangements to α‐Ferrocenyl Carbenium Ions

2017

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The reaction of FcCH2OH with chlorophosphates gave ferrocenyl phosphates FcCH2OP(O)(OR)2 [Fc = Fe(η5‐C5H5)(η4‐C5H4)], which readily separate into phosphate anions and ferrocenyl carbo‐cations. The latter species undergoes consecutive reactions, for example, electrophilic aromatic substitutions. When nitriles, instead of alcohols, are treated with FcLi or tBuLi and chlorophosphates, chiral‐pool based ferrocenylimino phosphoramidates Fc‐CR=N‐P(O)(OR*)2 are formed, which are promising candidates for anionic homo phospho‐Fries rearrangements. Moreover, the sterically demanding chiral chlorophosphate with R* enabled oxidative couplings of the imines to form a diferrocenylazine. Similarly, the reaction of Fc–Li with 9‐anthrylnitrile produced a 10‐ferrocenyl‐substituted product, contrary to a reaction at the C≡N functionality. A planar‐chiral ortho‐P(S)Ph2‐functionalized ferrocenylmethanol also gave carbo‐cations under acidic conditions. These species can be sulfurized in a unique way giving thio ethers, whereby the in situ formed 1,2‐P(S)Ph2,CH2+ ferrocene cation acts as the sulfur and electron source. However, lowering the substrate concentration prevents sulfur migration, resulting in electrophilic substitution reactions with aromatic solvents. Planar‐chiral ferrocenylmethyl thio or anisyl derivatives were applied as ligands in Pd‐catalyzed Suzuki–Miyaura C,C cross‐couplings for the atroposelective synthesis of hindered biaryls with up to 26 % ee at low catalyst loadings (1 mol‐% Pd).

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Section: Electrochemistrymentioning

confidence: 99%

(Planar‐Chiral) Ferrocenylmethanols: From Anionic Homo Phospho‐Fries Rearrangements to α‐Ferrocenyl Carbenium Ions

2017

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“…Up to date, several mechanism, e.g. S N reactions, radicalic couplings or rearrangements have been reported for the synthesis of selanes, whereby S N Ar reactions are limited to a few examples , . The transfer of a single Se atom, as observed for the synthesis of rac ‐ 19 , is unique and the first example for this type of selane formation at a sterically demanding ortho ‐substituted ferrocene.…”

Section: Resultsmentioning

confidence: 99%

Reactivity of Planar‐Chiral α‐Ferrocenyl Carbocations towards Electron‐Rich Aromatics

et al. 2019

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The reaction of the enantiopure, planar‐chiral α‐ferrocenyl carbocation (Sp)‐2‐(P(=S)Ph2)FcCH2+ (Fc = Fe(η5‐C5H5)(η5‐C5H3)) towards electron‐rich arenes C6H5E (E = NH2, NMe2, NiPr2, NPh2, PPh2, P(=S)Ph2, OH, SH, SMe) regarding either a nucleophilic attack of the group E or an electrophilic aromatic substitution reaction of the arene at the CH2+ unit is reported. It was found that the amino, oxo or thio functionalities gave the respective ferrocenes in various product distributions, while the P‐based species didn't. Appropriate thiophosphine derivatives could be reduced to their PIII species that were applied as supporting ligands in atropselective C,C cross‐coupling reactions for the synthesis of sterically hindered biaryls, where sandwich compound (Sp)‐1‐(PPh2)‐2‐(o‐NMe2‐C6H4)CH2‐Fc gave an ee of 69 % (1 mol‐% [Pd]), which is up to date the highest observed value for planar‐chiral ferrocenes. The absolute configuration of the chiral ferrocenes was confirmed by single‐crystal X‐ray diffraction analysis. For seleno phosphane 1‐(P(=Se)Ph2)‐2‐(CH2OH)‐Fc a unique Se single‐atom transfer occurred within its reaction with Sanger's reagent. The presence of two chemically different Se atoms in 1‐(P(=Se)Ph2)‐2‐(((2,4‐(NO2)2‐C6H3)Se)CH2)‐Fc was confirmed by 77Se{1H} NMR spectroscopy and single‐crystal X‐ray diffraction analysis, respectively.

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ChemInform Abstract: Unexpected Acid‐Catalyzed Ferrocenylmethylation of Diverse Nucleophiles with Vinyloxymethylferrocene.

et al. 2016

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Unexpected acid-catalyzed ferrocenylmethylation of diverse nucleophiles with vinyloxymethylferrocene

Cited by 13 publications

References 50 publications

(Planar‐Chiral) Ferrocenylmethanols: From Anionic Homo Phospho‐Fries Rearrangements to α‐Ferrocenyl Carbenium Ions

(Planar‐Chiral) Ferrocenylmethanols: From Anionic Homo Phospho‐Fries Rearrangements to α‐Ferrocenyl Carbenium Ions

Reactivity of Planar‐Chiral α‐Ferrocenyl Carbocations towards Electron‐Rich Aromatics

ChemInform Abstract: Unexpected Acid‐Catalyzed Ferrocenylmethylation of Diverse Nucleophiles with Vinyloxymethylferrocene.

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