Increasing the Efficiency of the Transannular Diels–Alder Strategy via Palladium(II)-Catalyzed Macrocyclizations

Iafe, Robert G.; Kuo, Jonathan L.; Hochstatter, Dustin G; Saga, Tomomi; Turner, Jonathan W.; Merlic, Craig A.

doi:10.1021/ol303394t

Cited by 23 publications

(19 citation statements)

References 32 publications

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“…9−11 In 2013, Merlic and co-workers developed a new method to synthesize a range of cyclic trienes and dienynes by Pd(II)-catalyzed macrocyclizations (Scheme 1). 12,13 This method enables the syntheses of a broad range of macrocycles that contain diene and dienophile joined by two tethers.…”

Section: ■ Introductionmentioning

confidence: 99%

“…12 The macrocycles in eqs 1−3a are 12-membered rings with cis-alkenyl, trans-alkenyl, and alkynyl dienophiles; the macrocycle in eq 3b also contains an alkynyl dienophile, and the oxygen atoms are replaced by nitrogen atoms in the tethers. None of the 12-membered macrocycles were isolable and instead directly gave the tricyclic cycloaddition products in high yields (Scheme 2 eqs 1−3).…”

Section: ■ Introductionmentioning

confidence: 99%

“…We also observed high reactivities for 12-membered macrocycles containing either alkene (1 and 3) or alkyne (5a,b) dienophiles. 12,13 The rates of Diels−Alder reactions are usually lower for macrocycles with alkyne dienophiles due to the higher LUMO energies of the dienophiles, but both alkenes and alkynes react readily in these cases.…”

Section: ■ Introductionmentioning

confidence: 99%

“…12,13 Although the reactivities of the cis/trans isomers of C14 trienes have been explored previously, there have been few systematic theoretical studies of TADA reactivities concerning the effects of ring size, and no work has been done on how the types of atoms in the macrocycles modulate reactivities. 15−17 We studied the energetics and transition structures of this series of TADA reactions in order to delineate the origins of the reactivities and stereoselectivities.…”

Section: ■ Introductionmentioning

confidence: 99%

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Distortion, Tether, and Entropy Effects on Transannular Diels–Alder Cycloaddition Reactions of 10–18-Membered Rings

Chen

Patel

et al. 2015

J. Org. Chem.

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Density functional theory calculations were performed on a set of 13 transannular Diels−Alder (TADA) reactions with 10−18-membered rings. The results were compared with those for bimolecular and intramolecular Diels−Alder reactions in order to investigate the controlling factors of the high TADA reactivities. The effects of tether length, heteroatoms, and alkynyl dienophiles on reactivity were analyzed. We found a correlation between tether length and reactivity, specifically with 12-membered macrocycles undergoing cycloaddition most readily. Furthermore, modifying 12-membered macrocycles by heteroatom substitution and utilizing alkynyl dienophiles enhances the reaction rates up to 10 5 -fold.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Distortion, Tether, and Entropy Effects on Transannular Diels–Alder Cycloaddition Reactions of 10–18-Membered Rings

Chen

Patel

et al. 2015

J. Org. Chem.

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“…We prepared the new PBZyn probe starting with the known 4-(propargyloxy)-2-buten-1-ol ( 5 , Fig. 1 B [ 35 ] using a combination of published procedures [ 24 , 30 ], as shown in Fig. 1 B.…”

Section: Resultsmentioning

confidence: 99%

A clickable probe for versatile characterization of S-nitrosothiols

et al. 2020

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S-nitrosation of cysteine thiols (SNOs), commonly referred to as S-nitrosylation, is a cysteine oxoform that plays an important role in cellular signaling and impacts protein function and stability. Direct labeling of SNOs in cells with the flexibility to perform a wide range of cellular and biochemical assays remains a bottleneck as all SNO-targeted probes to date employ a single analytical modality such as biotin or a specific fluorophore. We therefore developed a clickable, alkyne-containing SNO probe ‘PBZyn’ based on the o-phosphino-benzoyl group warhead that enables multi-modal analysis via click conjugation. We demonstrate the utility of PBZyn to assay SNOs using in situ cellular imaging, protein blotting and affinity purification, as well as mass spectrometry. The flexible PBZyn probe will greatly facilitate investigation into the regulation of SNOs.

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Copper‐Catalyzed β‐Selective Hydroborylation of Ynamides: A Facile Access to (E)‐β‐Alkenylamide Boronates

et al. 2015

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AC u-catalyzed, highly b-selective borylation of ynamides with bis(pinacolato)diboron as the hydroboration reagent is reported, giving (E)-b-alkenylamide boronates in excellent regio-and stereoselectivity under mild reaction conditions, whichp rovides ac omplementary regioselectivity to the existing methods.Alkenylboronates are versatile synthetic intermediates and valuable reagents in organic synthesis because of their applicability toward ad iversea rray of chemical transformations, including transition-metal-catalyzedc ross-coupling reactions.[1] In this context, the hydroboration of alkynes, with or without promoters, has become one of the most straightforwarda nd efficient methods for producing these molecules. [2][3][4] It should be noted, however, that most of the previousr eports focus on the transformation of terminal acetylenes, [2][3][4] while only limited examples of the hydroboration of unsymmetrical internal alkynes have been demonstrated, [5] mainly duet ot he low reactivity or unsatisfactory regio-and stereoselectivity.A ss uch, the development of regiocontrolled hydroboration of internal alkynes still remainst ob eexplored.Besidesa cetylenic esters, [5g, h] ac lass of activated alkynes, severaln on-activated, unsymmetrical, internal acetylenes have recently emerged as effective substrates for the regioselective hydroboration reactiono wing to recentd evelopments in the Cu-catalyzed hydroboration process. For example, Ts uji and coworkers [6] developeda ne legant regiodivergenth ydroboration of 1-aryl-1-alkynes by the choice of organoboron reagents, pinacolborane (HBpin) or bis(pinacolato)diboron (B 2 pin 2 ).[7] Ar egiocontrolled hydroborationo fp ropargylic-functionalized internal alkynes was realized by Arrayµs,C arreteroa nd co-workers.[8] Meanwhile, the McQuade group reported ar egio-and stereoselective hydroboration of propargylic alcohol derivatives to yield a-o rb-borylated products by matching substrates and copper catalysts.[9] We have also accomplished aC u-catalyzed regioselective hydroboration of thioalkynesf or the divergent construction of (Z)-1-thio-and (Z)-2-thio-1-alkenyl boronates, in which the SR group plays ak ey role in determining the regioselectivity (Scheme1).[10a]On the other hand, the regiocontrolled hydroboration of ynamides constitutes as ignificant challenge because of the readilyp rotonolysiso fC ÀBb onds of the resulting alkenylamide boronates, [11a] until ar ecent report by Zhu and co-workers, [11b] in which they developed aC u-catalyzed a-selective borylationo fy namides with readily available B 2 pin 2 as the hydroborating reagent. In contrast, there is no general method for the regioselective b-borylation of ynamides.[12] Undoubtedly, the realizationo facomplementary regioselective method to the precedentm ethods is of considerable importance.H erein, we presento ur resultso nC u-catalyzed hydroboration of ynamides [13] with B 2 pin 2 for the effective synthesis of stereodefined (E)-b-alkenylamide boronates under mild reaction conditions. Compared ...

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Increasing the Efficiency of the Transannular Diels–Alder Strategy via Palladium(II)-Catalyzed Macrocyclizations

Cited by 23 publications

References 32 publications

Distortion, Tether, and Entropy Effects on Transannular Diels–Alder Cycloaddition Reactions of 10–18-Membered Rings

Distortion, Tether, and Entropy Effects on Transannular Diels–Alder Cycloaddition Reactions of 10–18-Membered Rings

A clickable probe for versatile characterization of S-nitrosothiols

Copper‐Catalyzed β‐Selective Hydroborylation of Ynamides: A Facile Access to (E)‐β‐Alkenylamide Boronates

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