Area of research
Materials Chemistry · Organic Chemistry
Research interest
Research topics from publications: Alkyne Origami: Folding Oligoalkynes into Polyaromatics; Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry; Radical Alkyne peri‐Annulation Reactions for the Synthesis of Functionalized Phenalenes, Benzanthrenes, and Olympicene; Twofold π-Extension of Polyarenes via Double and Triple Radical Alkyne peri -Annulations: Radical Cascades Converging on the Same Aromatic Core; Twofold π-Extension of Polyarenes via Double and Triple Radical Alkyne peri-Annulations: Radical Cascades Converging on the Same Aromatic Core. Representative work: Do not bend the triple bonds! This familiar undergraduate mantra must be disobeyed if the alkyne group is used as a building block in molecular construction. This Account will describe our exploits in "alkyne origami", that is, folding oligoalkynes into new shapes via cyclization cascades. This research stems from a set of guidelines for the cyclizations of alkynes that we suggested in 2011 ( Gilmore Chem. Rev. 2011 , 111 , 6513 ; Alabugin J. Am. Chem. Soc. 2011 , 133 , 12608 ). The guidelines blended critical analysis of ∼40 years of experimental research with computations into the comprehensive predictions of the relative favorability of dig-cyclizations of anions and radicals. In this Acc The high energy packed in alkyne functional group makes alkyne reactions highly thermodynamically favorable and generally irreversible. Furthermore, the presence of two orthogonal π-bonds that can be manipulated separately enables flexible synthetic cascades stemming from alkynes. Behind these "obvious" traits, there are other more subtle, often concealed aspects of this functional group's appeal. This review is focused on yet another interesting but underappreciated alkyne feature: the fact that the CC alkyne unit has the same oxidation state as the -CH2C(O)- unit of a typical carbonyl compound. Thus, "classic carbonyl chemistry" can be accessed through alkynes, and new transformations can
Twofold π-Extension of Polyarenes via Double and Triple Radical Alkyne <i>peri</i> -Annulations: Radical Cascades Converging on the Same Aromatic Core
Twofold π-Extension of Polyarenes via Double and Triple Radical Alkyne peri-Annulations: Radical Cascades Converging on the Same Aromatic Core
Twofold π-Extension of Polyarenes via Double and Triple Radical Alkyne peri-Annulations: Radical Cascades Converging on the Same Aromatic Core
Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry
Alkyne Origami: Folding Oligoalkynes into Polyaromatics
Radical Alkyne <i>peri</i>‐Annulation Reactions for the Synthesis of Functionalized Phenalenes, Benzanthrenes, and Olympicene
Radical Alkyne <i>peri</i>‐Annulation Reactions for the Synthesis of Functionalized Phenalenes, Benzanthrenes, and Olympicene