Efficient Multicomponent Synthesis of α-Trifluoromethyl Proline, Homoproline, and Azepan Carboxylic Acid Dipeptides

Gulevich, Anton V.; Shevchenko, Nikolay E.; Баленкова, Е. С.; Roeschenthaler, Gerd‐Volker; Nenajdenko, Valentine G.

doi:10.1055/s-0028-1087529

Cited by 17 publications

(4 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is, to our knowledge, the first example of 1,4 asymmetric induction in an isocyanide based multicomponent reaction of chiral carbonyl compounds or imines, and the first example of diastereoselective Ugi reaction on chiral seven-membered imines [20–21]. …”

Section: Resultsmentioning

confidence: 99%

Long-range diastereoselectivity in Ugi reactions of 2-substituted dihydrobenzoxazepines

Banfi¹,

Basso²,

Cerulli³

et al. 2011

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryThe Ugi reaction of 2-substituted dihydrobenzoxazepines was found to proceed with unexpectedly good diastereoselectivitiy (diastereoisomeric ratios up to 9:1), despite the large distance between the pre-existing stereogenic centre and the newly generated one. This result represents the first good 1,4 asymmetric induction in an Ugi reaction as well as the first example of diastereoselective Ugi reaction of seven membered cyclic imines. It allows the diversity-oriented synthesis of various tetrahydro[f][1,4]benzoxazepines.

show abstract

Section: Resultsmentioning

confidence: 99%

Long-range diastereoselectivity in Ugi reactions of 2-substituted dihydrobenzoxazepines

Banfi¹,

Basso²,

Cerulli³

et al. 2011

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…Thus, when 13 was treated with an isocyanide (RNC) in the presence of CF 3 CO 2 H, piperidine 16 was formed via intermediate V (Scheme 10, eq. 1) [17]. It is worth mentioning that an azido-Ugi reaction was performed using isocyanate (RNC) in the presence of TMSN 3 in MeOH.…”

Section: From Cyclic Substratesmentioning

confidence: 99%

Synthesis of Substituted α-Trifluoromethyl Piperidinic Derivatives

Rioton¹,

Pardo²,

Cossy³

2017

Molecules

View full text Add to dashboard Cite

A comprehensive survey of pathways leading to the generation of α-trifluoromethyl monocyclic piperidinic derivatives is provided (65 references). These compounds have been synthesized either from 6-membered rings e.g., pipecolic acid or lactam derivatives by introduction a trifluoromethyl group, from pyridine or pyridinone derivatives by reduction, and from 5-membered rings e.g., prolinol derivatives by ring expansion, from linear amines by cyclization or from dienes/dienophiles by [4 + 2]-cycloaddition.

show abstract

“…There is a rich portfolio of fluorine-containing proline analogues that have been developed to date (Figure 1B): fluorinated [6][7][8][9][10][11][12], trifluoromethylated [13][14][15][16][17][18][19][20][21][22][23], chimeric [16,19,[24][25][26][27][28][29], conformationally restricted [30][31][32][33] having variations in the ring size [34][35][36][37][38][39], non-α [40][41][42][43][44], and other analogues [45][46][47][48]. The fluorine-containing functional groups are usually chemically inert under most biologically relevant conditions.…”

Section: Introductionmentioning

confidence: 99%

Polarity effects in 4-fluoro- and 4-(trifluoromethyl)prolines

Kubyshkin¹

2020

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

Fluorine-containing analogues of proline are valuable tools in engineering and NMR spectroscopic studies of peptides and proteins. Their use relies on the fundamental understanding of the interplay between the substituents and the main chain groups of the amino acid residue. This study aims to showcase the polarity-related effects that arise from the interaction between the functional groups in molecular models. Properties such as conformation, acid–base transition, and amide-bond isomerism were examined for diastereomeric 4-fluoroprolines, 4-(trifluoromethyl)prolines, and 1,1-difluoro-5-azaspiro[2.4]heptane-6-carboxylates. The preferred conformation on the proline ring originated from a preferential axial positioning for a single fluorine atom, and an equatorial positioning for a trifluoromethyl- or a difluoromethylene group. This orientation of the substituents explains the observed trends in the pK a values, lipophilicity, and the kinetics of the amide bond rotation. The study also provides a set of evidences that the transition state of the amide-bond rotation in peptidyl-prolyl favors C4-exo conformation of the pyrrolidine ring.

show abstract

Efficient Multicomponent Synthesis of α-Trifluoromethyl Proline, Homoproline, and Azepan Carboxylic Acid Dipeptides

Cited by 17 publications

References 5 publications

Long-range diastereoselectivity in Ugi reactions of 2-substituted dihydrobenzoxazepines

Long-range diastereoselectivity in Ugi reactions of 2-substituted dihydrobenzoxazepines

Synthesis of Substituted α-Trifluoromethyl Piperidinic Derivatives

Polarity effects in 4-fluoro- and 4-(trifluoromethyl)prolines

Contact Info

Product

Resources

About