Stereoselective synthesis of spirofused 3-substituted 2,3,4,4a,5,6-hexahydro- 6H-benzo[c]quinolizine using the tert-amino effect

Deeva, E. V.; Глухарева, Т. В.; Ткачев, А. В.; Morzherin, Yu. Yu.

doi:10.1070/mc2006v016n02abeh002247

Cited by 9 publications

(2 citation statements)

References 8 publications

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“…If an asymmetric carbon atom is present in the tert -amino group, the isomerizations may proceed diastereoselectively. ,, In some cases, a new chiral center is formed, and enantiomerically pure 1,2,3,4-tetrahydroquinolinic systems can be afforded from chiral substrates. − In all the above examples, the stereoselectivity of the T-reactions was due to the presence of an asymmetric carbon atom in a starting reactant.…”

Section: Introductionmentioning

confidence: 99%

Diastereoselective T-Reaction of 1-Alkyl-5-(5-nitro-2-N-morpholino-benzylidene)barbituric Acids in the Solid State: Synthesis of 1-Alkyl-2,4,6-trioxoperhydropyrimidino-5-spiro-10′-(7′-nitro-1′,3′,4′,9′,10′,10a′-hexahydro-2′-oxa)-4a′-azaphenanthrenes and Their 2′-Thia Analogues

Краснов

Khrustalev

2014

Crystal Growth & Design

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1-Alkyl-5-(5-nitro-2-N-morpholinobenzylidene) barbituric acids undergo tert-amino effect reactions (T-reactions) yielding 1-alkyl-2,4,6-trioxoperhydropyrimidino-5-spiro-10′-(7′-nitro-1′,3′,4′,9′,10′,10a′hexahydro-2′-oxa)-4a′-azaphenanthrene derivatives as a mixture of (S*,S*)-and (S*,R*)-diastereomers. A novel heterophase modification of the T-reaction is proposed, which makes it possible to afford nearly pure (S*,S*)-diastereomers in high yields, whereas rearrangement reactions in solutions usually lack stereoselectivity. To our best knowledge, this is the first example of deliberate tuning stereodirection of a T-reaction by external conditions. Using X-ray diffraction analysis, we demonstrate that this diastereoselectivity of the solid state T-reaction is due to a peculiar crystal structure of starting 5-arylidene barbiturates, which accommodates only one specific conformation fixed by a strong intramolecular C−H•••π interaction.

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Section: Introductionmentioning

confidence: 99%

Diastereoselective T-Reaction of 1-Alkyl-5-(5-nitro-2-N-morpholino-benzylidene)barbituric Acids in the Solid State: Synthesis of 1-Alkyl-2,4,6-trioxoperhydropyrimidino-5-spiro-10′-(7′-nitro-1′,3′,4′,9′,10′,10a′-hexahydro-2′-oxa)-4a′-azaphenanthrenes and Their 2′-Thia Analogues

Краснов

Khrustalev

2014

Crystal Growth & Design

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“…It was thus found that the cyclization by tert-amino effect mechanism occurred diastereoselectively when there was a substituent at the β-carbon atom in the dialkylamino group. [40,41]. …”

Section: -97%mentioning

confidence: 99%

tert-Amino effect: the Meth-Cohn and Reinhoudt reactions (Review)

Platonova

Глухарева

Zimovets

et al. 2013

Chem Heterocycl Comp

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The term "tert-amino effect" was proposed in 1972 [1] for the cyclization reactions of tertiary anilines containing various double bonds at the ortho position. Meth-Cohn and Suschitzky [1] referred to the first observation of the tert-amino effect by Pinnow in 1895 [2]. Many different examples of reactions involving the tert-amino effect have now accumulated, and it clearly is a convenient method for the synthesis of an impressive number of nitrogen-containing heterocycles that otherwise might be difficult to obtain. Reviews were published by Reinhoudt in 1990 [3] and by Meth-Cohn in 1996 [4] on heterocyclization reactions that take place by the mechanism of the tert-amino effect. Another review dedicated to 1,6-and 1,8-naphthiridine derivatives was published in 2003 by Quintela [5]. In the review [6] that we published in 2005, attention was focused on the use of such reactions for the synthesis of spiro compounds. In the review [7], published in 2006, the cyclization reactions of ortho-vinylanilines and their heterocyclic aza analogs were considered, and classification according to the method of ring formation was proposed.

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Stereoselective Synthesis of Spirofused 3‐Substituted 2,3,4,4a,5,6‐Hexahydro‐6H‐benzo[c]quinolizine Using the tert‐Amino Effect.

Deeva¹,

Глухарева²,

Ткачев

et al. 2006

ChemInform

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Fused pyridine derivatives R 0450Stereoselective Synthesis of Spirofused 3-Substituted 2,3,4,4a,5,6-Hexahydro--6H-benzo[c]quinolizine Using the tert-Amino Effect. -Reactions of benzaldehyde (I) and cyclic CH-active compounds (II) occur as a tandem of Knoevenagel condensation and cyclization by a tert-amino effect to give the title benzoquinolizines (III) with complete stereoselectivity. Contrary, cyclization of compound (V) derived from (I) and malononitrile yields the expected benzoquinolizine as 1:1 mixture of diastereomers. -(DEEVA, E. V.; GLUKHAREVA, T. V.; TKACHEV, A. V.; MORZHERIN*, Y. Y.; Mendeleev Commun. 2006, 2, 82-83; Dep. Technol. Org. Synth., Urals State Tech. Univ., Ekaterinburg 620002, Russia; Eng.) -M. Kowall 37-128

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Stereoselective synthesis of spirofused 3-substituted 2,3,4,4a,5,6-hexahydro- 6H-benzo[c]quinolizine using the tert-amino effect

Cited by 9 publications

References 8 publications

Diastereoselective T-Reaction of 1-Alkyl-5-(5-nitro-2-N-morpholino-benzylidene)barbituric Acids in the Solid State: Synthesis of 1-Alkyl-2,4,6-trioxoperhydropyrimidino-5-spiro-10′-(7′-nitro-1′,3′,4′,9′,10′,10a′-hexahydro-2′-oxa)-4a′-azaphenanthrenes and Their 2′-Thia Analogues

Diastereoselective T-Reaction of 1-Alkyl-5-(5-nitro-2-N-morpholino-benzylidene)barbituric Acids in the Solid State: Synthesis of 1-Alkyl-2,4,6-trioxoperhydropyrimidino-5-spiro-10′-(7′-nitro-1′,3′,4′,9′,10′,10a′-hexahydro-2′-oxa)-4a′-azaphenanthrenes and Their 2′-Thia Analogues

tert-Amino effect: the Meth-Cohn and Reinhoudt reactions (Review)

Stereoselective Synthesis of Spirofused 3‐Substituted 2,3,4,4a,5,6‐Hexahydro‐6H‐benzo[c]quinolizine Using the tert‐Amino Effect.

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