The chemistry of cyclopropenone. Reactions at the carbon-carbon double bond.

Oda, Masaji; Breslow, Ronald; Pecoraro, J.

doi:10.1016/s0040-4039(01)94330-8

Cited by 26 publications

(7 citation statements)

References 2 publications

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“…It is also interesting to compare our results with those obtained from the reaction of cyclopropenone and DPIBF by Breslow and co-workers . Here, the [4 + 2] cycloaddition affords only the exo -adduct.…”

supporting

confidence: 61%

Cyclopropene: A New Simple Synthesis and Diels−Alder Reactions with Cyclopentadiene and 1,3-Diphenylisobenzofuran

et al. 1996

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supporting

confidence: 61%

Cyclopropene: A New Simple Synthesis and Diels−Alder Reactions with Cyclopentadiene and 1,3-Diphenylisobenzofuran

et al. 1996

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“…Various reactions of this simplest aromatic ketone were subsequently studied. [18,19] The discovery and study of the cyclopropenyl cation was actually not my first adventure in aromaticity. Before high school I was doing various experiments in my basement lab and Max Tishler, a family friend and Director of Chemistry at Merck, gave me a copy of the organic textbook by Conant and Blatt when I was in 7th grade.…”

Section: Aromaticitymentioning

confidence: 99%

“…The resulting dichlorocyclopropenes hydrolyzed in water to the parent cyclopropenone. Various reactions of this simplest aromatic ketone were subsequently studied …”

Section: Nozoe and Isnamentioning

confidence: 99%

Novel Aromatic and Antiaromatic Systems

Breslow

2014

The Chemical Record

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Note from the Editor: August Kekulé's dream and his theory of the structure of benzene (1865). Julius Thomsen's logic that benzene contains equivalent electrons between its carbon atoms (ca. 1900). Richard Willstätter's synthesis and observation that 1,3,5,7‐cyclooctatetraene is not aromatic (early 1900s). Sir Robert Robinson's proposal of the ‘aromatic sextet’ (1925). Erich Hückel's molecular orbital treatment of benzene and other unsaturated compounds that separated sigma and pi electrons (early 1930s). Tetsuo Nozoe and Michael Dewar's independent proposal of a new aromatic structure for a cycloheptatrieneone (mid‐1940s). Ronald Breslow's demonstration that cyclopropenyl cation is aromatic (1958). Breslow's proposal of ‘antiaromaticity’ (1965). I offer several comments. First, in the field of aromaticity, Breslow is in mighty exceptional company. Second, his research has extended well beyond aromaticity. Yes, Breslow is applying the concepts of antiaromaticity toward the development of highly conductive organic materials. But his research has encompassed enzyme mimics, remote functionalization reactions, unnatural DNA analogues and cancer chemotherapy. Indeed, Breslow is the co‐discoverer of a highly successful drug, Vorinostat, which is FDA‐approved for the treatment of cutaneous T‐cell lymphoma. We thank Professor Breslow for joining our project honoring his and our friend, Tetsuo Nozoe. Tetsuo Nozoe would have would have been deeply touched. —Jeffrey I. Seeman Guest Editor University of Richmond Richmond, Virginia 23173, USA E‐mail: jseeman@richmond.edu Ronald Breslow with Koji Nakanishi (left) and Tetsuo Nozoe (center), Sendai, 1970. Abstract We contributed to the field of non‐benzenoid aromatic compounds by creating the cyclopropenyl cation and various of its derivatives, including cyclopropenone; it was the first aromatic system with other than six pi electrons in a single ring, and the simplest aromatic system. The pioneering work of Tetsuo Nozoe in tropolone chemistry was celebrated with the founding of ISNA, the International Symposium on Non‐Benzenoid Aromatic Compounds, where I described our work in the field. It fit the prediction that aromaticity would be found in systems with 4n + 2 pi electrons, where n is an integer. I was also concerned with the properties of monocyclic systems with 4n cyclically conjugated pi electrons. They were expected not to be aromatic, but the interesting question was whether they were actually antiaromatic, especially destabilized by the cyclic conjugation in such 4n species as the cyclopropenyl anion, cyclobutadiene, and cyclopentadienyl cation. The evidence supports antiaromaticity in these cases. We also examined compounds where 4n cyclic pi systems were fused with aromatic systems, and most interestingly systems in which two 4n pi systems were fused. In these cases the periphery of the molecules had 4n + 2 pi electrons, for aromaticity, but the components were antiaromatic. Recently we have studied electrical conductivities in aromatic molecules such as thiophe...

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“…Interesting application of such a endo‐ selectivity of DA cycloaddition adduct to afford distinctly selective products under suitable reagent condition was reported by Breslow and co‐worker in 1972 (see Figure 3). [30] …”

Section: Introductionmentioning

confidence: 99%

“…Interesting application of such a endo-selectivity of DA cycloaddition adduct to afford distinctly selective products under suitable reagent condition was reported by Breslow and co-worker in 1972 (see Figure 3). [30] Moreover, one of the key advances for illustrating endo-exo selectivity was published by Bosnich in 1978 [31] where thermally induced Diels-Alder cycloaddition between cyclopentadiene and monodeuterated enol acetate furnished a mixture of endo: exo isomers in 60 : 40 ratio. To identification of the structure and assignment of stereochemistry, both the isomers were separated using alkaline hydrolysis followed by iodolactonization, which executed only when carboxylate group occupies an endo position.…”

Section: Introductionmentioning

confidence: 99%

Regioselectivity Switch Towards the Development of Innovative Diels‐Alder Cycloaddition and Productive Applications in Organic Synthesis

2022

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The Diels‐Alder (DA) reaction is one of the fascinating synthetic strategies known for its pericyclic action and concerted mechanism that leads to various targets. Numerous synthetic pursuits have been rewarded with conceptually distinct and efficient ways. To date, extensive and spectacular accomplishments have been made in the field of Diels‐Alder chemistry to overcome the complexities of organic synthesis that inspired organic chemists to focus on expanding and establishing the postulates. In principle, DA reactions are governed by their straightforward reactivity pattern with a high degree of certainty, primarily attributed to the HOMO‐LUMO separation of reacting partners. Furthermore, general forecasts rely on account of background studies, conveniently hypothesizing the stereochemical outcomes and reaction dynamic pathways. DA has recently emerged as a technique for establishing a variety of products from the same reacting species under varying reaction conditions rather than a general reactivity profile. Such exceptional results are of significant interest in organic synthesis to pursue the challenges of unanticipated product establishment. Herein, we summarize the impressive finding of the remarkable switch in the regioselectivity and diastereoselectivity of DA reactions under a diverse set of reaction protocols in light of Diels‐Alder's unending importance in chemical science. This review aims to establish a beneficial account of Diels‐Alder towards the astonishing switches extended to study varying synthetic versions in organic synthesis protocols attributed to natural and biologically active scaffolds. This review also provides insight into distinct reaction dynamics in DA reactions that are subjected to access molecular frameworks ranging from simple to complicated ones to foster high levels of innovation in chemical sciences.

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The chemistry of cyclopropenone. Reactions at the carbon-carbon double bond.

Cited by 26 publications

References 2 publications

Cyclopropene: A New Simple Synthesis and Diels−Alder Reactions with Cyclopentadiene and 1,3-Diphenylisobenzofuran

Cyclopropene: A New Simple Synthesis and Diels−Alder Reactions with Cyclopentadiene and 1,3-Diphenylisobenzofuran

Novel Aromatic and Antiaromatic Systems

Regioselectivity Switch Towards the Development of Innovative Diels‐Alder Cycloaddition and Productive Applications in Organic Synthesis

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