Synthesis of Chiral Fluorinated Amino Acids by Eosin Y Catalyzed Perfluoroalkyl Radical Addition to Dehydroamino Acids

Yajima, Tomoko; Ikegami, Mako

doi:10.17677/fn20714807.2018.06.01

Cited by 7 publications

(24 citation statements)

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“…Asymmetric synthesis of the fluorinated α-AA derivatives 45 by conjugate addition of carbon radicals generated by photoactivation to a chiral substrate 44 and the isolation of α-AA 46 (Yajima, 2013(Yajima, , 2018). [99,104] leucine (27 b) and phosphinothricin analogues were isolated with excellent enantioselectivities and yields of up to 83% by decomposition of the obtained Ni(II) complexes with aqueous HCl. [124] The mechanism of the reaction was proposed based on Baran's work.…”

Section: Belokon's Chiral Nickel(ii) Complexes Of Dehydroalanine Schimentioning

confidence: 99%

“…[95] In 2013 Yajima group disclosed a promising and practical protocol for the asymmetric synthesis of fluorinated α-AAs. [99,104] The photoinduced radical hydroperfluoroalkylation of an N-phtaloyl derivative of Oppolzer's camphorsultam 44 using tris(trimethylsilyl) silane (TTMSS) as an H-donor and Na 2 S 2 O 3 as reductant resulted in the corresponding products 45 in good yields (up to 90%) with excellent distereoselectivities (up to > 99:1 dr) (Scheme 23). [99] Later, in 2018, the authors improved the developed method by using Eosin Y as a photosensitizer and visible light that favours more practicability.…”

Section: Other Chiral Substrates Featuring a Dehydroalanine Moietymentioning

confidence: 99%

“…[99] Later, in 2018, the authors improved the developed method by using Eosin Y as a photosensitizer and visible light that favours more practicability. [104] Finally, an adduct 45 with R f = CF 3 was transformed into the corresponding (S)-β-trifluoromethyl alanine 46 Scheme 37. Asymmetric synthesis of the α-AA derivatives 79 and 80 by conjugate addition of radicals to the chiral substrates 77 and 78 (Bertrand, 1998).…”

Section: Other Chiral Substrates Featuring a Dehydroalanine Moietymentioning

confidence: 99%

“…Then, the final stereoselective protonation of anion by water molecule resulted in the corresponding hydroperfluoroalkylated product 45 (Scheme 23). [104] An efficient and practical asymmetric synthesis of non-proteinogenic α-AAs with γ-quaternary carbon centres was reported by Fu group in 2016 (Scheme 24). [101] The selective intermolecular olefinolefin coupling of an Evans-type (S)-4-tert-butyloxazolidin-2-one 47 with different olefins (including cyclic ones) catalysed by inexpensive iron(III) acetylacetonate and phenyl silane as the reductant provided the corresponding diastereomeric adducts (S,S)-48 in a ratio of up to > 20:1 dr and in moderate to good yields (40-88%) (Scheme 24).…”

Section: Other Chiral Substrates Featuring a Dehydroalanine Moietymentioning

confidence: 99%

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Advances in Asymmetric Amino Acid Synthesis Enabled by Radical Chemistry

2020

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Chiral amino acids (AAs), being the main "building" blocks of the living organisms, are also an important class of organic compounds which broadly applied in synthetic chemistry, biochemistry, catalysis and the designing of new drugs. According to the industrial-commodity market, chiral non-proteinogenic AAs containing various functional groups come to the fore. To date, radical cross-coupling reactions are becoming an option as an attractive powerful tool for AA syntheses. Owing to mild reaction conditions and high functional-group tolerance, radical chemistry represents an ideal strategy for the synthesis of challenging complex non-proteinogenic AAs. Moreover, the radical cross-coupling allows introducing AA residue into drug scaffolds and natural compounds. In the present review, we wish to summarize and discuss all the reported to date methods of the asymmetric synthesis of AAs using radical chemistry by presenting a comprehensive account of the literature in this field going back to 1990. We especially emphasize on a radical chemistry approach and, exclusively, on stereoselective synthesis of various α-, β-, γ-AAs and derivatives employing a different type of radical initiators starting from AIBN and organostannes and ending with powerful photoredox catalysis. Furthermore, the mechanism of the reported reactions will be discussed. Radicals Generated from AA Derivatives in Conjugate Additions 6.1. Radicals Generated from α-Substituted Glycine Derivatives in AA Synthesis 6.2. Modification of Chiral AA Side Chain by Radical Chemistry 7.

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Section: Belokon's Chiral Nickel(ii) Complexes Of Dehydroalanine Schimentioning

confidence: 99%

Section: Other Chiral Substrates Featuring a Dehydroalanine Moietymentioning

confidence: 99%

Section: Other Chiral Substrates Featuring a Dehydroalanine Moietymentioning

confidence: 99%

Section: Other Chiral Substrates Featuring a Dehydroalanine Moietymentioning

confidence: 99%

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Advances in Asymmetric Amino Acid Synthesis Enabled by Radical Chemistry

2020

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“…To date, there exist a plethora of methods for the synthesis of FAAs, [19–23] however, the approaches for obtaining of PFAAs are still rare, especially in an enantioselective manner [24,25] . As a consequence, only several selective examples of asymmetric synthesis of PFAAs have been reported to date [26–33] . For example, Yajima et al .…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of Perfluoroalkylated α‐Amino Acids through Generated Radicals Using a Chiral Ni(II) Complex

Stoletova

Moshchenkov

Smol’yakov

et al. 2020

Helvetica Chimica Acta

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Dedicated to our friend and colleague Prof. Antonio Togni on the occasion of his 65th birthday Perfluoroalkylated α-amino acids (PFAAs) are a unique class of compounds for biochemistry and pharmaceutical science. In this context, we report the successful intermolecular coupling of the Belokon's chiral dehydroalanine Ni(II) complex with a variety of perfluoroalkyl iodides. A 4-cyanopyridine/B 2 Pin 2 catalytic system generates perfluoroalkyl radicals, which after trapping by the ligand sphere of a chiral Ni(II) complex provide the diastereomeric complexes with up to > 20 : 1 dr (seven examples). The obtained major (S,S)-diastereomers were easily isolated by simple silica column chromatography in 33-54 % yields. The perfluoroalkylated α-AA was subsequently released from the obtained Ni(II) complex through aqueous HCl treatment. The chiral auxiliary ligand ((S)-BPB = (S)-2-(N-benzylprolyl)aminobenzophenone) can be easily recycled after the acidic complex decomposition and reused for the synthesis of the starting dehydroalanine Ni(II) complex.

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Synthesis of Short Peptides with Perfluoroalkyl Side Chains and Evaluation of Their Cellular Uptake Efficiency

et al. 2023

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With an increasing demand for macromolecular biotherapeutics, the issue of their poor cell‐penetrating abilities requires viable and relevant solutions. Herein, we report tripeptides bearing an amino acid with a perfluoroalkyl (RF) group adjacent to the α‐carbon. RF‐containing tripeptides were synthesized and evaluated for their ability to transport a conjugated hydrophilic dye (Alexa Fluor 647) into the cells. RF‐containing tripeptides with the fluorophore showed high cellular uptake efficiency and none of them were cytotoxic. Interestingly, we demonstrated that the absolute configuration of perfluoroalkylated amino acids (RF‐AAs) affects not only nanoparticle formation but also the cell permeability of the tripeptides. These novel RF‐containing tripeptides are potentially useful as short and noncationic cell‐penetrating peptides (CPPs).

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Synthesis of Chiral Fluorinated Amino Acids by Eosin Y Catalyzed Perfluoroalkyl Radical Addition to Dehydroamino Acids

Cited by 7 publications

References 0 publications

Advances in Asymmetric Amino Acid Synthesis Enabled by Radical Chemistry

Advances in Asymmetric Amino Acid Synthesis Enabled by Radical Chemistry

Asymmetric Synthesis of Perfluoroalkylated α‐Amino Acids through Generated Radicals Using a Chiral Ni(II) Complex

Synthesis of Short Peptides with Perfluoroalkyl Side Chains and Evaluation of Their Cellular Uptake Efficiency

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