A novel tert-amino effect based approach to 1,2,3,4-tetrahydroquinoline-2-spirocycloalkanes

Tverdokhlebov, Anton V.; Gorulya, Alexander P.; Tolmachev, Andrey A.; Kostyuk, Alexander; Chernega, Alexander N.; Русанов, Эдуард Б.

doi:10.1016/j.tet.2006.07.042

Cited by 16 publications

(5 citation statements)

References 54 publications

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“…Other examples of the use of tert -amino effect for the synthesis of tetrahydroquinoline derivatives include the synthesis of 1,2,3,4-tetrahydroquinoline-2-spirocycloalkanes, and barbituric acid attached 3-spiro-tetrahydroquinolines. , Other advances in this reaction are the use of microwave assistance for cyclization reactions carried out in solution and also under solvent-free conditions …”

Section: Synthesis Of 1234-tetrahydroquinolines Involving the Generat...mentioning

confidence: 99%

Advances in the Chemistry of Tetrahydroquinolines

2011

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Involving the Generation of Two Bonds 5.1. Introduction 5.2. Formation of the NÀC 2 and C 3 ÀC 4 Bonds 5.2.1. DielsÀAlder Related Reactions 5.2.2. Tandem Michael AdditionÀCyclization Sequence 5.2.3. Miscellaneous Reactions 5.3. Formation of the NÀC 2 and C 4 ÀC 4a Bonds 5.3.1. Michael Addition Initiated Reactions 5.3.2. Miscellaneous Reactions 5.4. Formation of the NÀC 2 and C 2 ÀC 3 Bonds 5.5. Formation of the C 2 ÀC 3 and C 3 ÀC 4 Bonds 5.6. Formation of the C 2 ÀC 3 and C 4 ÀC 4a Bonds 5.7. Formation of the C 3 ÀC 4 and C 4 ÀC 4a Bonds 5.8. Formation of the C 8a ÀN and C 4 ÀC 4a Bonds 5.9. Formation of the NÀC 2 and C 8a ÀN Bonds 6. Synthesis of 1,2,3,4-Tetrahydroquinolines Involving the Generation of Three or More Bonds 6.1. Formation of the NÀC 2 , C 2 ÀC 3 , and C 4 ÀC 4a Bonds: The Povarov and Related Reactions

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Section: Synthesis Of 1234-tetrahydroquinolines Involving the Generat...mentioning

confidence: 99%

Advances in the Chemistry of Tetrahydroquinolines

2011

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“…In addition to the above works, the [1,5]-hydride shift strategy can also be used for the construction of spirocyclic tetrahydroquinolines containing cycloalkane units. In 2006, Tverdokhlebov and co-authors disclosed an interaction of ortho -aminobenzaldehydes 189 with substituted acetonitriles 190 promoted by Et 3 N in EtOH to yield tetrahydroquinoline-2-spirocycloalkanes 192 with high yields ( Scheme 20 ) ( Tverdokhlebov et al, 2006 ). According to the tert -amino effect mechanism, the reaction was assumed to move forward via sequential Knoevenagel condensation/[1,5]-hydrogen shift/ring closure of the formed adduct.…”

Section: The Construction Of a Spiro-tetrahydroquinoline Skeleton Con...mentioning

confidence: 99%

The Cascade [1,5]-Hydride Shift/Intramolecular C(sp3)–H Activation: A Powerful Approach to the Construction of Spiro-Tetrahydroquinoline Skeleton

Quan

Xie

et al. 2022

Front. Chem.

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The direct functionalization of inert C–H bonds is regarded as one of the most powerful strategies to form various chemical bonds and construct complex structures. Although significant advancements have been witnessed in the area of transition metal-catalyzed functionalization of inert C–H bonds, several challenges, such as the utilization and removal of expensive transition metal complexes, limited substrate scope and large-scale capacity, and poor atom economy in removing guiding groups coordinated to the transition metal, cannot fully fulfill the high standard of modern green chemistry nowadays. Over the past decades, due to its inherent advantage compared with a transition metal-catalyzed strategy, the hydride shift activation that applies “tert-amino effect” into the direct functionalization of the common and omnipresent C(sp3)–H bonds adjacent to tert-amines has attracted much attention from the chemists. In particular, the intramolecular [1,5]-hydride shift activation, as the most common hydride shift mode, enables the rapid and effective production of multifunctionally complex frameworks, especially the spiro-tetrahydroquinoline derivatives, which are widely found in biologically active natural products and pharmaceuticals. Although great accomplishments have been achieved in this promising field, rarely an updated review has systematically summarized these important progresses despite scattered reports documented in several reviews. Hence, in this review, we will summarize the significant advances in the cascade [1,5]-hydride shift/intramolecular C(sp3)-H functionalization from the perspective of “tert-amino effect” to build a spiro-tetrahydroquinoline skeleton, and the content is categorized by structure type of final spiro-tetrahydroquinoline products containing various pharmaceutical units. Besides, current limitations as well as future directions in this field are also pointed out. We hope our review could provide a quick look into and offer some inspiration for the research on hydride shift strategy in the future.

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“…Another approach to the synthesis of the spiro compounds was described by Ukrainian scientists [48]. During the cyclization of compounds 55 containing methyl and cycloalkyl groups at the nitrogen atom, only the spiro compounds 56 were formed.…”

Section: -80%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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A novel tert-amino effect based approach to 1,2,3,4-tetrahydroquinoline-2-spirocycloalkanes

Cited by 16 publications

References 54 publications

Advances in the Chemistry of Tetrahydroquinolines

Advances in the Chemistry of Tetrahydroquinolines

The Cascade [1,5]-Hydride Shift/Intramolecular C(sp3)–H Activation: A Powerful Approach to the Construction of Spiro-Tetrahydroquinoline Skeleton

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

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