Asymmetric Metal‐Templated Route to Amino Acids with 3‐Spiropyrrolidine Oxindole Core via a 1,3‐Dipolar Addition of Azomethine Ylides to a Chiral Dehydroalanine Ni(II) Complex

Asymmetric Metal‐Templated Route to Amino Acids with 3‐Spiropyrrolidine Oxindole Core via a 1,3‐Dipolar Addition of Azomethine Ylides to a Chiral Dehydroalanine Ni(II) Complex Full article

Journal

Advanced Synthesis & Catalysis
ISSN: 1615-4169 , E-ISSN: 1615-4150

Output data

Year: 2022, Volume: 364, Number: 14, Pages: 2395-2402 Pages count : 8 DOI: 10.1002/adsc.202200446

Authors

Gugkaeva Zalina T. ¹ , Panova Maria V. ² , Smolyakov Alexander F. ^1,3 , Medvedev Michael G. ² , Tsaloev Alan T. ⁴ , Godovikov Ivan A. ¹ , Maleev Victor I. ¹ , Larionov Vladimir A. ^1,5

Affiliations

1	A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), Vavilov Str. 28, 119991 Moscow, Russian Federation
2	N.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences, Leninsky prospect 47, 119991 Moscow, Russian Federation
3	Plekhanov Russian University of Economics, Stremyanny per. 36, 117997 Moscow, Russian Federation
4	Chemical Diversity Research Institute, Rabochaya Str. 2a, 141400 Khimki, Moscow Region, Russian Federation
5	Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklaya Str. 6, 117198 Moscow, Russian Federation

We herein developed a protocol for the asymmetric synthesis of artificial AAs featuring a 3-spiropyrrolidine oxindole skeletal with continuous tetrasubstituted carbon stereocenters by a 1,3-dipolar cycloaddition reaction of in situ generated azomethine ylides with a chiral dehydroalanine Ni(II) complex. A three-component reaction of the Ni(II) complex with various isatins and AAs in green solvent (ethanol) provided series of diastereomeric complexes with high dr (>20:1) in 40–86% yields. The formation of different regioisomers in the case of sarcosine and proline was explained using quantum chemical calculation. The acidic decomposition of the obtained Ni(II) complexes led to the target unnatural complex AAs with a 3-spiropyrrolidine oxindole core. The chiral auxiliary ligand was recovered after decomposition and reused for the synthesis of the starting dehydroalanine complex-substrate.

Gugkaeva Z.T. , Panova M.V. , Smolyakov A.F. , Medvedev M.G. , Tsaloev A.T. , Godovikov I.A. , Maleev V.I. , Larionov V.A.
Asymmetric Metal‐Templated Route to Amino Acids with 3‐Spiropyrrolidine Oxindole Core via a 1,3‐Dipolar Addition of Azomethine Ylides to a Chiral Dehydroalanine Ni(II) Complex
Advanced Synthesis & Catalysis. 2022. V.364. N14. P.2395-2402. DOI: 10.1002/adsc.202200446 WOS Scopus OpenAlex

≡ Web of science:	WOS:000817201800001
≡ Scopus:	2-s2.0-85132908220
≡ OpenAlex:	W4283168989