Scalable Synthesis of Piperazines Enabled by Visible‐Light Irradiation and Aluminum Organometallics

Suárez‐Pantiga, Samuel; Colas, Kilian; Johansson, Magnus J.; Mendoza, Abraham

doi:10.1002/anie.201505608

Cited by 25 publications

(20 citation statements)

References 79 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[35i] Modification of the tpa ligand to form ad inuclear,r igid complex has been found to retain the oxidative activity but to suppress significantly the nonproductive formation of m-oxo dimers ([Fe(L3) 2 ] 4 + ). [54] Beller [35b, c, 55] and Bolm [56] have shown that in situ formed iron complexes with simple amine/picolinic acid derivatives or amino alcohols as ligands are capable of stereoselective oxidations. More recently, an in situ assembled hexadentate iron complex has been demonstratedt o catalyzee fficientlym etal-based aliphatic CÀHo xidation ([Fe(L4) 2 ](OTf) 2 ).…”

Section: Novel Catalystdesignmentioning

confidence: 99%

Biologically Inspired C−H and C=C Oxidations with Hydrogen Peroxide Catalyzed by Iron Coordination Complexes

Olivo

Cussó

Costas

2016

Chemistry An Asian Journal

View full text Add to dashboard Cite

The development of catalysts for the selective oxidation of readily available hydrocarbons or organic precursors into oxygenated products is a long-standing goal in organic synthesis. In the last decade, some iron coordination complexes have shown the potential to fit this role. These catalysts can mimic the O-O activation mode of far more sophisticated iron oxygenase enzymes, generating powerful yet selective oxidants. In this review, we report state-of-the-art C-H and C=C oxidations catalyzed by non-heme iron complexes and H O as the oxidant. Finally, we briefly describe some novel oxidative reactivity and the perspectives of this chemistry.

show abstract

Section: Novel Catalystdesignmentioning

confidence: 99%

Biologically Inspired C−H and C=C Oxidations with Hydrogen Peroxide Catalyzed by Iron Coordination Complexes

Olivo

Cussó

Costas

2016

Chemistry An Asian Journal

View full text Add to dashboard Cite

show abstract

“…[1,2] Processes involving the allene moiety together with another hydrocarbon unsaturation have attractedc onsiderable attention recently. [1,2] Processes involving the allene moiety together with another hydrocarbon unsaturation have attractedc onsiderable attention recently.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insight into Enantioselective Palladium‐Catalyzed Oxidative Carbocyclization–Borylation of Enallenes

Qiu

Mendoza

Posevins

et al. 2018

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The asymmetric palladium-catalyzed oxidative carbocyclization-borylation of enallenes, employing a chiral phosphoric acid as co-catalyst, constitutes an efficient and convenient entry into functionalized building blocks with cyclopentene scaffolds in high enantiopurity. Up till now there has been a lack of knowledge concerning the origin of enantioselectivity of this reaction as well as the absolute configuration of the product. Herein, we report the crystal structure of one of the compounds generated via this carbocyclization, providing the link between the configuration of the products and the configuration of the chiral phosphoric acid used in the reaction. Furthermore, the origin of the enantioselectivity is thoroughly investigated with density functional theory (DFT) calculations. By careful examination of different possible coordination modes, it is shown that the chiral phosphoric acid and the corresponding phosphate anion serve as ligands for palladium during the key stereoselectivity-determining cyclization step. In addition, we examine reactions wherein an extra chiral reagent, a p-benzoquinone containing a chiral sulfoxide, is used. The combined experimental and theoretical studies provide insight into the details of complexation of palladium with various species present in the reaction mixture, furnishing a general understanding of the factors governing the stereoselectivity of this and related catalytic reactions.

show abstract

“…At present, organolithiums do not engage in this reaction. On the sulfoxide side, substrates bearing aferrocene (2j), [22] as well as thiomorpholine (2m)a nd thioflavanone heterocycles (2s,t), further expand the potential of this reaction to impact ligand [3,23] and drug design. [1b, 24] Remarkably, b-heteroatoms and even unprotected ketones are tolerated (2m,s,t), further suggesting the unusual organometallic species which enable this reaction (entries 4a nd 5; Scheme 2a).…”

mentioning

confidence: 99%

Intermolecular Pummerer Coupling with Carbon Nucleophiles in Non‐Electrophilic Media

2017

Self Cite

View full text Add to dashboard Cite

A new Pummerer-type C-C coupling protocol is introduced based on turbo-organomagnesium amides, which unlike traditional Pummerer reactions, does not require strong electrophilic activators, engages a broad range of C(sp )-, C(sp )-, and C(sp)-nucleophiles, and seamlessly integrates with C-H and C-X magnesiation. Given the central character of sulfur compounds in organic chemistry, this protocol allows access to unrelated carbonyls, olefins, organometallics, halides, and boronic esters through a single strategy.

show abstract

Scalable Synthesis of Piperazines Enabled by Visible‐Light Irradiation and Aluminum Organometallics

Cited by 25 publications

References 79 publications

Biologically Inspired C−H and C=C Oxidations with Hydrogen Peroxide Catalyzed by Iron Coordination Complexes

Biologically Inspired C−H and C=C Oxidations with Hydrogen Peroxide Catalyzed by Iron Coordination Complexes

Mechanistic Insight into Enantioselective Palladium‐Catalyzed Oxidative Carbocyclization–Borylation of Enallenes

Intermolecular Pummerer Coupling with Carbon Nucleophiles in Non‐Electrophilic Media

Contact Info

Product

Resources

About