Asymmetric Organocatalytic Thio-Diels–Alder Reactions via Trienamine Catalysis

Jiang, Hao; Cruz, David Cruz; Li, Yang; Lauridsen, Vibeke Henriette; Jørgensen, Karl Anker

doi:10.1021/ja4007244

Cited by 86 publications

(29 citation statements)

References 74 publications

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“…[53] Theuse of adienophile with an ucleophilic site enabled a[ 4 + +2] cycloaddition with trienamines followed by ring closure,d emonstrating an e,b,ipsoreactivity pattern. Thea pplication of 2,4-dienals and cyanoacrylamides illustrated the high levels of molecular complexity that can be obtained with trienamine chemistry.T he bicyclicmolecules enabled the formation of five stereocenters and bicyclic structures in ao ne-pot reaction affording the products in 70-98 % ee.R ecently,h etero-Diels-Alder reactions of trienamines were also reported, [54] enabling the synthesis of optically active heterocycles containing either sulfur or nitrogen (Scheme 5).…”

Section: Trienamine Catalysismentioning

confidence: 99%

The Diarylprolinol Silyl Ethers: Ten Years After

et al. 2015

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Asymmetric organocatalysis has experienced an incredible development since the beginning of this century. The expansion of the field has led to a large number of efficient types of catalysts. One group, the diarylprolinol silyl ethers, was introduced in 2005 and has been established as one of the most frequently used in aminocatalysis. In this Minireview, we will take a look in the rear-view mirror, ten years after the introduction of the diarylprolinol silyl ethers. We will focus on the perspectives of the different activation modes made available by this catalytic system. Starting with a short introduction to aminocatalysis, we will outline the properties that have made the diarylprolinol silyl ethers a common choice of catalyst. Furthermore, we will describe the major tendencies in the activation and reaction concepts developed with regard to reactivity patterns and combinations with other activation concepts.

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Section: Trienamine Catalysismentioning

confidence: 99%

The Diarylprolinol Silyl Ethers: Ten Years After

et al. 2015

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“…As an example, as many as four new stereocenters can be prepared in a single step using the DA reaction (Scheme ). There are an enormous number of reports in which the DA reaction was applied for the synthesis of new materials and natural products . Quite recently, cyclopentadienes with Raman and electrochemically active tags were patterned covalently onto graphene surfaces using force‐accelerated DA reactions …”

Section: Introductionmentioning

confidence: 99%

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

Cui

Liu

2014

J of Physical Organic Chem

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The Diels-Alder (DA) reaction is one of the most important reactions in organic chemistry. The controversy surrounding this reaction as to whether it follows a concerted or stepwise mechanism has existed for a long time. The reaction of 1,3-butadiene and ethylene is the paradigmatic example of the DA reaction. We have reinvestigated the mechanism of this reaction using density functional theory. The theoretical study considered all types of possible pathways for the reaction of 1,3-butadiene and ethylene using six functionals at different rungs of Jacob's ladder. Therefore, a complete picture is given for a thorough understanding of the iconic DA reaction, and a new stationary point during the reaction processes has been reported for the first time. The calculated results indicated that three functionals, ωB97X-D, M06-2X, and B2-PLYP, of the fourth and fifth rungs of Jacob's ladder performed well in the investigation of the mechanism of this reaction and that the reliable basis set should be larger than 6-311+G(2d,p). The cis-1,3-butadiene more easily reacted with ethylene compared with 1,3-butadiene in the trans conformation. The concerted mechanism was found to be energetically favorable, whose energy barrier is around 10 kcal/mol lower than that of the stepwise mechanism. Two investigated solvents, toluene and CH 3 CN, had little impact on this simple DA reaction.

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“…15 In a recent study, the volume parameters of the reaction of thiobenzophenone with isoprene were determined, and on this basis the authors concluded that a concerted reaction mechanism is followed. 16 In recent reports, asymmetric thia-Diels-Alder reactions of activated dithioesters 17 as well as of aryl-and hetaryl thioketones 18 with an in-situ-generated chiral trienamine were presented. In the second case, a stepwise reaction mechanism via diradical intermediates was proposed.…”

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confidence: 99%

Thia-Diels–Alder reactions of hetaryl thioketones with nonactivated 1,3-dienes leading to 3,6-dihydro-2H-pyrans: evidence for a diradical mechanism

Mlostoń

Grzelak

Linden

et al. 2017

Chem Heterocycl Comp

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Dihetaryl thioketones possessing thiophen-2-yl and selenophen-2-yl rings react as "superdienophilic" reagents with nonactivated 1,3-dienes such as 2,3-dimethylbuta-1,3-diene, cyclopentadiene, and mixtures of isomeric hexa-2,4-dienes to produce the expected 2H-thiopyrans in moderate to excellent yields. In the latter case, the corresponding cis-2,2-dihetaryl-3,6-dimethyl-3,6-dihydro-2H-thiopyrans are formed as the sole products in a stereoconvergent thia-Diels-Alder reaction. A stepwise mechanism via delocalized diradical intermediates is postulated to rationalize the observed reaction course. Treatment of 4,5-dimethyl-2,2-di(thiophen-2-yl)-3,6-dihydro-2H-thiopyran with excess of m-CPBA at room temperature leads to the oxidation of the C=C bond and the sulfur atom in the six-membered ring.

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Asymmetric Organocatalytic Thio-Diels–Alder Reactions via Trienamine Catalysis

Cited by 86 publications

References 74 publications

The Diarylprolinol Silyl Ethers: Ten Years After

The Diarylprolinol Silyl Ethers: Ten Years After

A thorough understanding of the Diels–Alder reaction of 1,3‐butadiene and ethylene

Thia-Diels–Alder reactions of hetaryl thioketones with nonactivated 1,3-dienes leading to 3,6-dihydro-2H-pyrans: evidence for a diradical mechanism

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