Discovery of ZACA reaction − Zr-catalyzed asymmetric carboalumination of alkenes

Negishi, Ei‐ichi

doi:10.3998/ark.5550190.0012.803

Cited by 18 publications

(9 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…On the basis of Negishi’s work, known alcohol 15 was prepared in three steps from ( S )-(−)-citronellal ( 6 ) in 30% overall yield (Scheme ). Thanks to a Zr-catalyzed asymmetric carboalumination of alkene 14 (ZACA reaction), the anti -dimethyl system could be satisfactorily addressed.…”

Section: Results and Discussionmentioning

confidence: 99%

Synthetic Studies toward the Total Synthesis of Tautomycetin

et al. 2019

View full text Add to dashboard Cite

The studies culminating in the synthesis of two large subunits of tautomycetin are described. The first one, fragment C1-C12 that has an anti-1,3-dimethyl system and a terminal diene unit, was accomplished in 10 linear steps in 7.4% overall yield. The second one, fragment C13-C25 which bears the sensitive anhydride framework and the majority of the stereogenic centers, was prepared in 13 linear steps (longest sequence) in 8% overall yield. Among the key transformations used, a regioselective epoxide opening, a Pd-catalyzed addition of terminal alkyne to acceptor alkyne, a Mukaiyama aldol reaction, a Yamaguchi esterification and a homemade mild di-esterification can be cited. The chosen strategies allowed good yields, stereoselectivity, reproducibility and scalability for several important intermediates. Scheme 2. Synthesis of the anti-1,3-dimethyl system via the ZACA reaction. 18a

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Synthetic Studies toward the Total Synthesis of Tautomycetin

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Currently, photoluminescence (PL) properties have been studied for Ti-, Zr-, and Hf-based metallocene and post-metallocene complexes. [4][5][6][7][8][9][10] These complexes are used widely as catalysts in the chemistry of organoaluminium and organomagnesium compounds, [11][12][13][14][15][16][17][18][19][20] as well as in the synthesis of polyolefins. [21][22][23] As a rule, a moderate concentration of metal complexes in the catalytic system and, therefore, low content of catalytically active sites precludes the use of common physicochemical methods for studying reaction mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Photoluminescence and mechanoluminescence of solid‐state zirconocene dichlorides

et al. 2021

View full text Add to dashboard Cite

Spectral-luminescence properties of 23 samples of zirconium complexes were studied. Mechanoluminescence spectra of 10 complexes were obtained. The solid-state component of the mechanoluminescence spectrum, that is the luminescence of the crystal itself, coincided with the photoluminescence spectra of these complexes, which indicated identical emission from the same excited states in mechanoluminescence and photoluminescence, despite the different ways of excitation. The luminescence maximum was red shifted as substituents appeared in the ligand, in particular in the presence of a bridging group connecting π-ligands (ansa-complexes) and also for a substituted bis-indenyl complex rac-Me 2 Si(2-Me-4-Ph-5-OMe-6-Bu t -Ind) 2 ZrCl 2 ). It was found that mechanical destruction of the rac-isomer of complex Mе 2 С(2-Me-4-Bu t -C 5 H 2 ) 2 ZrCl 2 , unlike that of the meso-isomer, was accompanied by a more than a 10-fold increase in intensity and by a shift in the mechanoluminescence spectrum to longer wavelengths.

show abstract

“…The using of enantiomerically pure complexes as the catalysts afords the asymmetric induction in the reactions. Thus, the method of Zr-catalyzed asymmetric carboalumination of alkenes-ZACA-reaction has been developed [7][8][9][10][11]34], which was applied to the synthesis of a number of biologically active compounds. The involvement of methylaluminoxane (MAO) [35][36][37][38] or other Lewis acidic cocatalysts [39] substantially increases the activity of the catalytic systems providing alkene dimers, oligomers and polymers.…”

Section: Mechanisms Of Zirconocene Catalysis In Alkene Carbo-and Cyclmentioning

confidence: 99%

Alkene and Olefin Functionalization by Organoaluminum Compounds, Catalyzed with Zirconocenes: Mechanisms and Prospects

Parfenova¹,

Kovyazin²,

Tyumkina³

et al. 2018

Alkenes

View full text Add to dashboard Cite

Alkene and olein functionalization via addition of electro-or nucleophilic reagents is one of the convenient synthetic methods for the insertion of heteroatoms into organic molecules. The use of organometallic reagents in these reactions in combination with the speciic catalysts provides high substrate conversion and process selectivity. The introduction of this approach into the chemistry of organoaluminum compounds leads to the development of chemo-, regio-and stereoselective catalytic methods of alkene and olein functionalization. The chapter focuses on the modern concepts of the alkene hydro-, carbo-and cycloalumination mechanisms, that is, the experimental and theoretical data on the intermediate structures involved in the product formation, the efects of the catalyst and organoaluminum compound structure, reaction conditions on the activity and selectivity of the bimetallic systems. The prospects of the development of enantioselective methods using these catalytic systems for the alkene and olein transformations are considered.

show abstract

Discovery of ZACA reaction − Zr-catalyzed asymmetric carboalumination of alkenes

Cited by 18 publications

References 15 publications

Synthetic Studies toward the Total Synthesis of Tautomycetin

Synthetic Studies toward the Total Synthesis of Tautomycetin

Photoluminescence and mechanoluminescence of solid‐state zirconocene dichlorides

Alkene and Olefin Functionalization by Organoaluminum Compounds, Catalyzed with Zirconocenes: Mechanisms and Prospects

Contact Info

Product

Resources

About