Enantioselective Organocatalytic C−H Bond Functionalization via Tandem 1,5-Hydride Transfer/Ring Closure: Asymmetric Synthesis of Tetrahydroquinolines

Kang, Youngcheol; Kim, Sun Mi; Kim, Dae Young

doi:10.1021/ja103786c

Cited by 300 publications

(73 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[89] Indeed, the intramolecular reaction of a series of cinnamaldehyde derivatives 179a-e provided the corresponding ringfused tetrahydroquinolines 180a-e in moderate to excellent enantioselectivities of up to 99% ee combined with generally moderate yields and diastereoselectivities. A remarkable result was obtained for tetrahydroisoquinoline 179f.…”

Section: Domino Michael-intramolecular Alkylation Reactionsmentioning

confidence: 99%

Recent Developments in Asymmetric Organocatalytic Domino Reactions

2012

View full text Add to dashboard Cite

Since about the year 2000, the research area of asymmetric organocatalysis has grown rapidly to become one of the most fascinating and current fields in organic chemistry. In the last years, asymmetric domino reactions have widely benefited from this fast-growing field, as exemplified by the development of an explosive number of novel and powerful asymmetric organocatalytic domino processes, which allowed the easy construction of complex chiral molecular architectures from simple materials with high yields and very often remarkable enantioselectivities in a metal-free environment. Indeed, the possibility to join two or more organocatalytic reactions in one asymmetric domino process has become a challenging goal for chemists, due to several advantages from economical and environmental points of view, avoiding costly protecting groups and time-consuming purification procedures after each step, for example. This review aims to update the latest developments of this hot and fascinating field, covering the literature since the beginning of 2009.

show abstract

Section: Domino Michael-intramolecular Alkylation Reactionsmentioning

confidence: 99%

Recent Developments in Asymmetric Organocatalytic Domino Reactions

2012

View full text Add to dashboard Cite

show abstract

“…However, the use of Lewis acids considerably accelerated [26,[58][59][60][61] cyclization by the tert-amino effect mechanism and made it possible to extend the applicability of the reaction [26,61]. It was also shown that using such acids as trifluoroacetic, HCl, HBr or (-)-camphorsulfonic acid allowed to cyclize the vinyl derivatives 72 containing only one withdrawing group at the double bond [57,62]. It was noted in the review [3] that for cyclization without a catalyst there should be at least two electron-withdrawing substituents in the vinyl group.…”

Section: -100%mentioning

confidence: 99%

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

Platonova

Глухарева

Zimovets

et al. 2013

Chem Heterocycl Comp

View full text Add to dashboard Cite

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.

show abstract

“…[4] Among the reported transformations, intramolecular redox processes for the direct functionalization of C sp 3 ÀH bonds that are a to heteroatoms are important for the synthesis of structurally diverse amine and ether derivatives. [5] Furthermore, since the pioneering work of Kim and co-workers, [6] there have many good results reported in the area of intramolecular redox processes for the direct enantioselective C sp 3 À H functionalization at positions a to nitrogen atoms. [7] However, examples of the corresponding enantioselective reaction of ethers are scarce.…”

mentioning

confidence: 99%

“…[10] The presence of a counterion that is more weakly coordinating than ClO 4 À would lead to an iminium ion with enhanced electrophilicity (Scheme 1), thus accelerating the hydride shift. The weakly coordinating anions, BF 4 À and SbF 6 À , have been effective for many catalytic reactions. [11] Therefore, substrate 1 a was treated with 7 (the hydrochloride salt of 6) together with either AgBF 4 or AgSbF 6 (Table 1, entries 7 and 8).…”

mentioning

confidence: 99%

Organocatalytic Asymmetric Direct CH Functionalization of Ethers: A Highly Efficient Approach to Chiral Spiroethers

Jiao

Zhang

et al. 2012

Angewandte Chemie

View full text Add to dashboard Cite

Spiroverbindungen: Eine organokatalytische asymmetrische C sp 3‐H‐Funktionalisierung racemischer cyclischer Ether in α‐Stellung gelingt in Gegenwart katalytischer Mengen eines Imidazolidinons und einer starken Säure. Der hoch enantioselektive Tandemprozess aus 1,5‐Hydridtransfer und Cyclisierung öffnet einen Zugang zu chiralen Spiroethern mit vielfältigen Strukturen (siehe Schema).

show abstract

Enantioselective Organocatalytic C−H Bond Functionalization via Tandem 1,5-Hydride Transfer/Ring Closure: Asymmetric Synthesis of Tetrahydroquinolines

Abstract: The first organocatalytic enantioselective intramolecular 1,5-hydride transfer/ring closure reaction is described. This redox neutral reaction cascade allows for the efficient formation of ring-fused tetrahydroquinolines in high enantioselectivities.

Cited by 300 publications

References 57 publications

Recent Developments in Asymmetric Organocatalytic Domino Reactions

Recent Developments in Asymmetric Organocatalytic Domino Reactions

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

Organocatalytic Asymmetric Direct CH Functionalization of Ethers: A Highly Efficient Approach to Chiral Spiroethers

Contact Info

Product

Resources

About