Use of dilithiomethane equivalent in a novel one-flask [2 + 1 + 2] cyclopentannulation reaction: a highly efficient total synthesis of (.+-.)-hirsutene.

Ramig, Keith; Kuzemko, M. A.; McNamara, Kevin; Cohen, Theodore

doi:10.1021/jo00033a013

Cited by 37 publications

(12 citation statements)

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confidence: 99%

“…1 Cyclizations are achieved through the intramolecular coupling of enolates derived from diesters 2 and diketones 3 as well as the intramolecular oxidative cross coupling of enolates derived from two different carbonyl precursors. 1b, d Intermolecular homocoupling reactions of enolates are straightforward and have a long history in organic chemistry. 2–5 Conversely, bimolecular heterocoupling of equimolar amounts of two enolates through single electron oxidation is more difficult and at best should result in 50% yield of the product.…”

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On the Nature of the Oxidative Heterocoupling of Lithium Enolates

Casey

Flowers

2011

J. Am. Chem. Soc.

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The coupling of enolates through single electron oxidation is one of the most direct routes to generating 1,4-dicarbonyls. Recent work on the intermolecular heterocoupling of equimolar amounts of two different enolates through single electron oxidation has shown that synthetically useful yields beyond those statistically predicted can be obtained. To determine the underlying basis for the selective formation of heterocoupled products, kinetic, 7Li NMR, and synthetic studies were performed. The collection of data obtained from these experiments show that the selective formation of heterocoupled products is a consequence of heteroaggregation of lithium enolates.

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confidence: 99%

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confidence: 99%

On the Nature of the Oxidative Heterocoupling of Lithium Enolates

Casey

Flowers

2011

J. Am. Chem. Soc.

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“…Keith and co-workers [ 66 ] achieved a highly efficient total synthesis of (±)-hirsutene ((±)- 7 ), by using dilithiomethane equivalent in a novel one-flask [2 + 1 + 2] cyclopentannulation reaction ( Scheme 12 ).…”

Section: Chemical Synthesismentioning

confidence: 99%

Linear Triquinane Sesquiterpenoids: Their Isolation, Structures, Biological Activities, and Chemical Synthesis

Qiu

Lan

et al. 2018

Molecules

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Linear triquinane sesquiterpenoids represent an important class of natural products. Most of these compounds were isolated from fungi, sponges, and soft corals, and many of them displayed a wide range of biological activities. On account of their structural diversity and complexity, linear triquinane sesquiterpenoids present new challenges for chemical structure identification and total synthesis. 118 linear triquinane sesquiterpenoids were classified into 8 types, named types I–VIII, based on the carbon skeleton and the position of carbon substituents. Their isolation, structure elucidations, biological activities, and chemical synthesis were reviewed. This paper cited 102 articles from 1947 to 2018.

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“…[xv] Notably, the groups of both Kise and Helmchen developed useful strategies for the stereocontrolled enantioselective synthesis of several lignans, such as ent -hinokinin ( 6 ), through the oxidative dimerization of Evans oxazolidinones. [xvi] In addition to natural product synthesis, Paquette and coworkers made use of an intramolecular oxidative enolate coupling in their elegant synthesis of the structurally unusual hemispheric hydrocarbon, C16 hexaquinacene ( 7 ).…”

Section: Introductionmentioning

confidence: 99%

Oxidative Coupling of Enolates, Enol Silanes, and Enamines: Methods and Natural Product Synthesis

2012

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The oxidative coupling of enolates, enol silanes, and enamines provides a direct method for the construction of useful 1,4-dicarbonyl synthons. Despite being first reported in 1935, with subsequent important advances beginning in the 1970’s, the development of this powerful reaction into a reliable methodology was somewhat limited. In recent years, there have been a number of reports from several research groups demonstrating advances in several neglected areas of oxidative coupling. This microreview summarizes these new advances in methodology and provides an overview of recent natural product syntheses that showcase the power of these transformations.

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Use of dilithiomethane equivalent in a novel one-flask [2 + 1 + 2] cyclopentannulation reaction: a highly efficient total synthesis of (.+-.)-hirsutene.

Cited by 37 publications

References 0 publications

On the Nature of the Oxidative Heterocoupling of Lithium Enolates

On the Nature of the Oxidative Heterocoupling of Lithium Enolates

Linear Triquinane Sesquiterpenoids: Their Isolation, Structures, Biological Activities, and Chemical Synthesis

Oxidative Coupling of Enolates, Enol Silanes, and Enamines: Methods and Natural Product Synthesis

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