The Synthesis of α,α-Disubstituted α-Amino Acids via Ichikawa Rearrangement

被引：25

作者：

Szczesniak, Piotr ^{[1
]}

Pieczykolan, Michal ^{[1
]}

Stecko, Sebastian ^{[1
]}

机构：

[1] Polish Acad Sci, Inst Organ Chem, Kasprzaka 44-52, PL-01224 Warsaw, Poland

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 81卷 / 03期

关键词：

DIPEPTIDYL-PEPTIDASE-I; TO-ISOCYANATE REARRANGEMENT; NEUROTENSIN RECEPTOR ANTAGONIST; CATALYTIC ASYMMETRIC-SYNTHESIS; PURINERGIC P2X(7) RECEPTOR; N-HETEROCYCLIC CARBENES; CHIRAL ALLYLIC AMINES; STEREOSELECTIVE-SYNTHESIS; SIGMATROPIC REARRANGEMENT; MEDICINAL CHEMISTRY;

D O I：

10.1021/acs.joc.5b02628

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An approach to alpha,alpha-disubstituted alpha-amino acids is reported. The key step is allyl cyanate-to-isocyanate rearrangement. As demonstrated, the resultant allyl isocyanates can be directly trapped with various nucleophiles, for instance, alcohols, amines, and organometallic reagents, to provide a broad range of N-functionalized allylamines. The developed method has been successfully applied in the synthesis of two bioactive peptides: 2-aminoadamantane-2-carboxylic acid derived P2X(7)-evoked glutamate release inhibitor and 4-amino-tetrahydropyranyl-4-carboxylic acid derived dipeptide GSK-2793660, which is currently in clinical trials as cathepsin C inhibitor for the treatment of cystic fibrosis, noncystic fibrosis bronchiectasis, ANCA-associated vasculitis and bronchiectasis.

引用

页码：1057 / 1074

页数：18

共 50 条

[1] Synthesis of protected, chiral α,α-disubstituted α-amino acids via a Beckmann rearrangement
Frutos, RP
Spero, DM
TETRAHEDRON LETTERS, 1998, 39 (17) : 2475 - 2478
[2] Stereocontrolled Synthesis of the Aminocyclopentitol Core of Jogyamycin via an Ichikawa Rearrangement Reaction
Gerstner, Nels C.
Schomaker, Jennifer M.
JOURNAL OF ORGANIC CHEMISTRY, 2019, 84 (21): : 14092 - 14100
[3] Synthesis of allylsilane-containing amino acids via the Claisen rearrangement
Mohamed, M
Brook, MA
TETRAHEDRON LETTERS, 2001, 42 (02) : 191 - 193
[4] Asymmetric synthesis of α-alkylated α-amino acids via Beckmann rearrangement.
Guan, X
Bebensee, S
Pellegrini, J
Georg, GI
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1998, 216 : U251 - U251
[5] Stereodivergent Synthesis of α,α-Disubstituted α-Amino Acids via Synergistic Cu/Ir Catalysis
Wei, Liang
Zhu, Qiao
Xu, Shi-Ming
Chang, Xin
Wang, Chun-Jiang
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (04) : 1508 - 1513
[6] Efficient Synthesis of Symmetrical α,α-Disubstituted β-Amino Acids and α,α-Disubstituted Aldehydes via Dialkylation of Nucleophilic β-Alanine Equivalent
Lin, Daizong
Deng, Guanghui
Wang, Jiang
Ding, Xiao
Jiang, Hualiang
Liu, Hong
JOURNAL OF ORGANIC CHEMISTRY, 2010, 75 (05): : 1717 - 1722
[7] Catalytic, asymmetric synthesis of α,α-disubstituted amino acids
Belokon', YN
Bhave, D
D'Addario, D
Groaz, E
Maleev, V
North, M
Pertrosyan, A
TETRAHEDRON LETTERS, 2003, 44 (10) : 2045 - 2048
[8] Enantioselective synthesis of α,β-disubstituted-β-amino acids
Sibi, MP
Prabagaran, N
Ghorpade, SG
Jasperse, CP
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (39) : 11796 - 11797
[9] Synthesis of novel α-substituted and α,α-disubstituted amino acids by rearrangement of ammonium ylides generated from metal carbenoids
Clark, JS
Middleton, MD
ORGANIC LETTERS, 2002, 4 (05) : 765 - 768
[10] Asymmetric synthesis of monosubstituted and α,α-disubstituted α-amino acids via diastereoselective glycine enolate alkylations
Williams, Robert M.
Im, Myeong-Nyeo
Journal of the American Chemical Society, 1991, 113 (24)

← 1 2 3 4 5 →