New Synthetic Technology for the Synthesis of Hindered α-Diazoketones via Acyl Mesylates

Nicolaou, K. C.; Baran, Phil S.; Zhong, Yong‐Li; Choi, Ha-Soon; Fong, Kin Chiu; He, Yan; Yoon, Won Hyung

doi:10.1021/ol990790l

Cited by 45 publications

(25 citation statements)

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“…36,37 Diazo compound 20 was synthesized according to the procedure of Nicolaou and co-workers. 38,39 Carboxylic acid 19 was smoothly converted to diazo compound 20 by activation with CH 3 SO 2 Cl in the presence of Et 3 N at 0 °C followed by reaction of the resulting mesylate with diazomethane in ether at 0 °C for 30 min. Arndt-Eistert homologation 40 was achieved by reaction of diazo compound 20 with silver benzoate in the presence of Et 3 N at 23 °C for 1 h to provide the methyl ester 21 in 49% yield.…”

Section: Resultsmentioning

confidence: 99%

Design, synthesis and in vitro splicing inhibition of desmethyl and carba-derivatives of herboxidiene

Ghosh

et al. 2016

Org. Biomol. Chem.

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Herboxidiene is a potent inhibitor of spliceosomes. It exhibited excellent anticancer activity against multiple human cancer cell lines. Herein, we describe an enantioselective synthesis of a desmethyl derivative and the corresponding carba-derivatives of herboxidiene. The synthesis involved Suzuki coupling of vinyl iodide with boronate as the key reaction. For the synthesis of carbo-derivatives, the corresponding optically active cyclohexane-1,3-dicarbonyl derivatives were synthesized using an enantioselective desymmetrization of meso-anhydride. The biological properties of these derivatives were evaluated in an in vitro splicing assay.

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Section: Resultsmentioning

confidence: 99%

Design, synthesis and in vitro splicing inhibition of desmethyl and carba-derivatives of herboxidiene

Ghosh

et al. 2016

Org. Biomol. Chem.

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“…These reactions included radical-based ring closures to form novel heterocycles, the introduction of unsaturation adjacent to carbonyl groups, 136 benzylic oxidations, 137 and a number of mild deprotection procedures. 138 Furthermore, the CP project led to the development of a mild and effective procedure for the synthesis of sterically hindered diazoketones from carboxylic acid mesylates, 139 a new method for the one-carbon homologation of aldehydes, 140 and several DMP-based technologies for the preparation and redeployment of reactive species such as p -quinones and o -azaquinones. 141 Additionally, solution and solid phase methods enabling the conversion of α-sulfonated ketones to a wide range of heterocyclic compounds and useful synthetic building blocks were developed.…”

Section: Highlights Of Contributions From the Author’s Laboratoriesmentioning

confidence: 99%

Constructing molecular complexity and diversity: total synthesis of natural products of biological and medicinal importance

et al. 2012

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The advent of organic synthesis and the understanding of the molecule as they occurred in the nineteenth century and were refined in the twentieth century constitute two of the most profound scientific developments of all time. These discoveries set in motion a revolution that shaped the landscape of the molecular sciences and changed the world. Organic synthesis played a major role in this revolution through its ability to construct the molecules of the living world and others like them whose primary element is carbon. Although the early beginnings of organic synthesis came about serendipitously, organic chemists quickly recognized its potential and moved decisively to advance and exploit it in myriad ways for the benefit of mankind. Indeed, from the early days of the synthesis of urea and the construction of the first carbon-carbon bond, the art of organic synthesis improved to impressively high levels of sophistication. Through its practice, today chemists can synthesize organic molecules—natural and designed—of all types of structural motifs and for all intents and purposes. The endeavor of constructing natural products—the organic molecules of nature—is justly called both a creative art and an exact science. Often called simply total synthesis, the replication of nature’s molecules in the laboratory reflects and symbolizes the state of the art of synthesis in general. In the last few decades a surge in total synthesis endeavors around the world led to a remarkable collection of achievements that covers a wide ranging landscape of molecular complexity and diversity. In this article, we present highlights of some of our contributions in the field of total synthesis of natural products of biological and medicinal importance. For perspective, we also provide a listing of selected examples of additional natural products synthesized in other laboratories around the world over the last few years.

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“…Simpler unhindered carboxylic acids are converted to the respective symmetrical anhydride. 199 Dicyclohexyl carbodiimides, 200 cyanuric acid, 201 IBCF, 202 and TBTU 203 can also be applied as activating agents, however the results obtained in general do not justify their application (Scheme 62, left). …”

Section: Reaction Scopementioning

confidence: 99%

3.19 The Wolff Rearrangement

Candeias

Trindade

Góis

et al. 2014

Comprehensive Organic Synthesis II

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New Synthetic Technology for the Synthesis of Hindered α-Diazoketones via Acyl Mesylates

Cited by 45 publications

References 10 publications

Design, synthesis and in vitro splicing inhibition of desmethyl and carba-derivatives of herboxidiene

Design, synthesis and in vitro splicing inhibition of desmethyl and carba-derivatives of herboxidiene

Constructing molecular complexity and diversity: total synthesis of natural products of biological and medicinal importance

3.19 The Wolff Rearrangement

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