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

被引：11

作者：

Stoletova, Nadezhda, V ^{[1
]}

Moshchenkov, Andrey D. ^{[1
,2
]}

Smol'yakov, Alexander F. ^{[1
]}

Gugkaeva, Zalina T. ^{[1
]}

Maleev, Victor, I ^{[1
]}

Katayev, Dmitry ^{[3
]}

Larionov, Vladimir A. ^{[1
,4
]}

机构：

[1] Russian Acad Sci INEOS RAS, AN Nesmeyanov Inst Organoelement Cpds, Vavilov Str 28, RU-119991 Moscow, Russia

[2] Dmitry Mendeleev Univ Chem Technol Russia, Russian Acad Sci, Higher Chem Coll, Miusskaya Sq 9, RU-125047 Moscow, Russia

[3] Swiss Fed Inst Technol, Swiss Fed Inst Technol, Dept Chem & Appl Biosci, Vladimir Prelog Weg 2, CH-8093 Zurich, Switzerland

[4] RUDN Univ, Peoples Friendship Univ Russia, Miklukho Maklaya Str 6, RU-117198 Moscow, Russia

来源：

HELVETICA CHIMICA ACTA | 2021年 / 104卷 / 01期

基金：

俄罗斯基础研究基金会;

关键词：

amino acids; perfluoroalkylated α -amino acid; asymmetric synthesis; chiral nickel(II) complex; perfluoroalkyl iodides; NICKEL(II) COMPLEX; MICHAEL ADDITION; FLUORINE; DEHYDROALANINE; DERIVATIVES; GLYCINE; HOMOLOGATION;

D O I：

10.1002/hlca.202000193

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Perfluoroalkylated alpha-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 alpha-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.

引用

页数：11

共 48 条

[1] Fluorinated phenylalanines: synthesis and pharmaceutical applications [J].

Awad, Laila F. ;

Ayoup, Mohammed Salah .

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2020, 16 :1022-1050

[2] DIASTEREOSELECTIVE RADICAL-ADDITION TO DERIVATIVES OF DEHYDROALANINE AND OF DEHYDROLACTIC ACID [J].

BECKWITH, ALJ ;

CHAI, CLL .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1990, (16) :1087-1088

[3] ASYMMETRIC-SYNTHESIS OF BETA-SUBSTITUTED ALPHA-AMINO-ACIDS VIA A CHIRAL NI-II COMPLEX OF DEHYDROALANINE [J].

BELOKON, YN ;

SAGYAN, AS ;

DJAMGARYAN, SM ;

BAKHMUTOV, VI ;

BELIKOV, VM .

TETRAHEDRON, 1988, 44 (17) :5507-5514

[4] GENERAL-METHOD OF DIASTEREOSELECTIVE AND ENANTIOSELECTIVE SYNTHESIS OF BETA-HYDROXY-ALPHA-AMINO ACIDS BY CONDENSATION OF ALDEHYDES AND KETONES WITH GLYCINE [J].

BELOKON, YN ;

BULYCHEV, AG ;

VITT, SV ;

STRUCHKOV, YT ;

BATSANOV, AS ;

TIMOFEEVA, TV ;

TSYRYAPKIN, VA ;

RYZHOV, MG ;

LYSOVA, LA ;

BAKHMUTOV, VI ;

BELIKOV, VM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (14) :4252-4259

[5] Synthesis of complex unnatural fluorine-containing amino acids [J].

Brittain, William D. G. ;

Lloyd, Carissa M. ;

Cobb, Steven L. .

JOURNAL OF FLUORINE CHEMISTRY, 2020, 239

[6] Perfluoroalkylative pyridylation of alkenes via 4-cyanopyridine-boryl radicals [J].

Cao, Jia ;

Wang, Guoqiang ;

Gao, Liuzhou ;

Chen, Hui ;

Liu, Xueting ;

Cheng, Xu ;

Li, Shuhua .

CHEMICAL SCIENCE, 2019, 10 (09) :2767-2772

[7] STEREOSELECTIVE RADICAL-ADDITION OF CARBON-CENTERED RADICALS TO THE DEHYDROALANINE MOIETY OF THE CHIRAL NICKEL(II) COMPLEX OF THE SCHIFFS BASE DERIVED FROM (S)-2-[N-(N'-BENZYLPROLYL)AMINO]BENZOPHENONE AND DEHYDROALANINE [J].

GASANOV, RG ;

ILINSKAYA, LV ;

MISHARIN, MA ;

MALEEV, VI ;

RAEVSKI, NI ;

IKONNIKOV, NS ;

ORLOVA, SA ;

KUZMINA, NA ;

BELOKON, YN .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1994, (22) :3343-3348

[8] Discovery and Evaluation of BMS-708163, a Potent, Selective and Orally Bioavailable γ-Secretase Inhibitor [J].

Gillman, Kevin W. ;

Starrett, John E., Jr. ;

Parker, Michael F. ;

Xie, Kai ;

Bronson, Joanne J. ;

Marcin, Lawrence R. ;

McElhone, Kate E. ;

Bergstrom, Carl P. ;

Mate, Robert A. ;

Williams, Richard ;

Meredith, Jere E., Jr. ;

Burton, Catherine R. ;

Barten, Donna M. ;

Toyn, Jeremy H. ;

Roberts, Susan B. ;

Lentz, Kimberley A. ;

Houston, John G. ;

Zaczek, Robert ;

Albright, Charles F. ;

Decicco, Carl P. ;

Macor, John E. ;

Olson, Richard E. .

ACS MEDICINAL CHEMISTRY LETTERS, 2010, 1 (03) :120-124

[9] 4-Fluorinated L-lysine analogs as selective i-NOS inhibitors: methodology for introducing fluorine into the lysine side chain [J].

Hallinan, EA ;

Kramer, SW ;

Houdek, SC ;

Moore, WM ;

Jerome, GM ;

Spangler, DP ;

Stevens, AM ;

Shieh, HS ;

Manning, PT ;

Pitzele, BS .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2003, 1 (20) :3527-3534

[10] Contribution of Organofluorine Compounds to Pharmaceuticals [J].

Inoue, Munenori ;

Sumii, Yuji ;

Shibata, Norio .

ACS OMEGA, 2020, 5 (19) :10633-10640

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