Synthesis of Quaternary-Carbon-Containing β2,2-Amino Acids by the RhI-Catalyzed Enantioselective Arylation of α-Substituted β-Nitroacrylates

Jo Hsuan Fang, Jia Hong Jian, Hao Ching Chang, Ting Shen Kuo, Way Zen Lee, Ping Yu Wu, Hsyueh Liang Wu

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

An enantioselective RhI-catalyzed conjugate addition reaction of α-substituted β-nitroacrylates with various arylboronic acids by using chiral RhIdiene catalysts is described for the first time. The addition reaction proceeds under mild conditions in a range of common organic solvents and additives, and it affords the corresponding quaternary-carbon-containing α,α-disubstituted β-nitropropionate products in up to 63 % yield and 99 % ee. Reaction of either (E)- or (Z)-β-nitroacrylates provided the same enantiomer of the product, and a range of esters and aryl groups were tolerated. To demonstrate the utility of the method, ethyl (R)-1,1-methyl-1-phenyl-3-nitropropionate, prepared herein, was converted to the non-proteinogenic β2,2-amino acid, (R)-2-(aminomethyl)-2-phenylpropanoic acid, and to the β2,2-lactam, (R)-3-methyl-3-phenylazetidin-2-one. In addition, a tripeptide, which comprised l-phenylalanine, l-alanine, and β2,2-amino acid 7, was also synthesized.

Original languageEnglish
Pages (from-to)1830-1838
Number of pages9
JournalChemistry - A European Journal
Volume23
Issue number8
DOIs
Publication statusPublished - 2017 Jan 1

Fingerprint

Addition reactions
Carbon
Amino Acids
Lactams
Acids
Enantiomers
Phenylalanine
Alanine
Organic solvents
Esters
Catalysts
3-nitropropionic acid

Keywords

  • amino acids
  • asymmetric catalysis
  • conjugate addition
  • diene ligands
  • rhodium

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis of Quaternary-Carbon-Containing β2,2-Amino Acids by the RhI-Catalyzed Enantioselective Arylation of α-Substituted β-Nitroacrylates. / Fang, Jo Hsuan; Jian, Jia Hong; Chang, Hao Ching; Kuo, Ting Shen; Lee, Way Zen; Wu, Ping Yu; Wu, Hsyueh Liang.

In: Chemistry - A European Journal, Vol. 23, No. 8, 01.01.2017, p. 1830-1838.

Research output: Contribution to journalArticle

@article{b939e1d5337d4423b5619df1a6af00df,
title = "Synthesis of Quaternary-Carbon-Containing β2,2-Amino Acids by the RhI-Catalyzed Enantioselective Arylation of α-Substituted β-Nitroacrylates",
abstract = "An enantioselective RhI-catalyzed conjugate addition reaction of α-substituted β-nitroacrylates with various arylboronic acids by using chiral RhIdiene catalysts is described for the first time. The addition reaction proceeds under mild conditions in a range of common organic solvents and additives, and it affords the corresponding quaternary-carbon-containing α,α-disubstituted β-nitropropionate products in up to 63 {\%} yield and 99 {\%} ee. Reaction of either (E)- or (Z)-β-nitroacrylates provided the same enantiomer of the product, and a range of esters and aryl groups were tolerated. To demonstrate the utility of the method, ethyl (R)-1,1-methyl-1-phenyl-3-nitropropionate, prepared herein, was converted to the non-proteinogenic β2,2-amino acid, (R)-2-(aminomethyl)-2-phenylpropanoic acid, and to the β2,2-lactam, (R)-3-methyl-3-phenylazetidin-2-one. In addition, a tripeptide, which comprised l-phenylalanine, l-alanine, and β2,2-amino acid 7, was also synthesized.",
keywords = "amino acids, asymmetric catalysis, conjugate addition, diene ligands, rhodium",
author = "Fang, {Jo Hsuan} and Jian, {Jia Hong} and Chang, {Hao Ching} and Kuo, {Ting Shen} and Lee, {Way Zen} and Wu, {Ping Yu} and Wu, {Hsyueh Liang}",
year = "2017",
month = "1",
day = "1",
doi = "10.1002/chem.201604120",
language = "English",
volume = "23",
pages = "1830--1838",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "8",

}

TY - JOUR

T1 - Synthesis of Quaternary-Carbon-Containing β2,2-Amino Acids by the RhI-Catalyzed Enantioselective Arylation of α-Substituted β-Nitroacrylates

AU - Fang, Jo Hsuan

AU - Jian, Jia Hong

AU - Chang, Hao Ching

AU - Kuo, Ting Shen

AU - Lee, Way Zen

AU - Wu, Ping Yu

AU - Wu, Hsyueh Liang

PY - 2017/1/1

Y1 - 2017/1/1

N2 - An enantioselective RhI-catalyzed conjugate addition reaction of α-substituted β-nitroacrylates with various arylboronic acids by using chiral RhIdiene catalysts is described for the first time. The addition reaction proceeds under mild conditions in a range of common organic solvents and additives, and it affords the corresponding quaternary-carbon-containing α,α-disubstituted β-nitropropionate products in up to 63 % yield and 99 % ee. Reaction of either (E)- or (Z)-β-nitroacrylates provided the same enantiomer of the product, and a range of esters and aryl groups were tolerated. To demonstrate the utility of the method, ethyl (R)-1,1-methyl-1-phenyl-3-nitropropionate, prepared herein, was converted to the non-proteinogenic β2,2-amino acid, (R)-2-(aminomethyl)-2-phenylpropanoic acid, and to the β2,2-lactam, (R)-3-methyl-3-phenylazetidin-2-one. In addition, a tripeptide, which comprised l-phenylalanine, l-alanine, and β2,2-amino acid 7, was also synthesized.

AB - An enantioselective RhI-catalyzed conjugate addition reaction of α-substituted β-nitroacrylates with various arylboronic acids by using chiral RhIdiene catalysts is described for the first time. The addition reaction proceeds under mild conditions in a range of common organic solvents and additives, and it affords the corresponding quaternary-carbon-containing α,α-disubstituted β-nitropropionate products in up to 63 % yield and 99 % ee. Reaction of either (E)- or (Z)-β-nitroacrylates provided the same enantiomer of the product, and a range of esters and aryl groups were tolerated. To demonstrate the utility of the method, ethyl (R)-1,1-methyl-1-phenyl-3-nitropropionate, prepared herein, was converted to the non-proteinogenic β2,2-amino acid, (R)-2-(aminomethyl)-2-phenylpropanoic acid, and to the β2,2-lactam, (R)-3-methyl-3-phenylazetidin-2-one. In addition, a tripeptide, which comprised l-phenylalanine, l-alanine, and β2,2-amino acid 7, was also synthesized.

KW - amino acids

KW - asymmetric catalysis

KW - conjugate addition

KW - diene ligands

KW - rhodium

UR - http://www.scopus.com/inward/record.url?scp=85007618898&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85007618898&partnerID=8YFLogxK

U2 - 10.1002/chem.201604120

DO - 10.1002/chem.201604120

M3 - Article

VL - 23

SP - 1830

EP - 1838

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 8

ER -