A Cascade Suzuki–Miyaura/Diels–Alder Protocol: Exploring the Bifunctional Utility of Vinyl Bpin

Cain, David L; McLaughlin, Calum; Molloy, John J.; Carpenter‐Warren, Cameron L.; Anderson, Niall A.; Watson, Allan J. B.

doi:10.1055/s-0037-1611228

Cited by 15 publications

(13 citation statements)

References 36 publications

(62 reference statements)

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“…The following compounds were prepared according to literature methods: [Ru(η 6 -naphthalene)(η 4 -1,5-cod)] ( 1 ), [Pd(PPh 3 ) 4 ], [PdCl 2 (PPh 3 ) 2 ] and [Pd 2 (dba) 3 ]·C 6 H 6 , ( E )-butadien-1-yl B(pin) ( 2a ), (1 E ,3 E )-penta-1,3-dien-1-yl B(pin) ( 2b ), and vinyl B(neo) ( 3j ) . Vinyl B(dan) ( 3i ) was prepared by modification of a literature method . Styrene- d 2 ( 3e - d 2 ) (99 atomD %) was prepared by Wittig reaction using CD 3 I and benzaldehyde .…”

Section: Methodsmentioning

confidence: 99%

Ru(0)-Catalyzed Regioselective Synthesis of Borylated-1,4- and -1,5-Diene Building Blocks

et al. 2022

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A new methodology for preparation of borylated-1,4-and -1,5-diene building blocks is established. Ru(0)-catalyzed cross-dimerization of (1E,3E)-penta-1,3-dien-1-ylboronic acid pinacolate ester (2b) with but-3-en-2-one (3a) selectively gives a borylated-1,4-diene product, (3E,6E)-5-methyl-(4,4,5,5-tetrameth-) also gives a borylated-1,4-diene product. These crossdimerizations give mono-borylated-1,4-dienes, yet cross-dimerizations using (1E,3E)-penta-1,3-dien-1-ylboronic acid pinacolate ester (2b) with vinyl B(dan) (3i) produce a diborylated-1,5diene. Selective formation of 1,6-diborylated-1,5-dienes is unprecedented, and a series of diborylated-1,5-dienes can be used as building blocks for Suzuki−Miyaura cross-coupling reactions. As an application of the present method, the formal synthesis of racbongkrekic acid, a strong inhibitor of the adenine nucleotide translocator, has been achieved.

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Section: Methodsmentioning

confidence: 99%

Ru(0)-Catalyzed Regioselective Synthesis of Borylated-1,4- and -1,5-Diene Building Blocks

et al. 2022

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“…Recently, Watson and co-workers reported a cascade protocol, which relied on the double reactivity of vinyl boropinacolate, including the Suzuki-Miyaura and Diels-Alder reactions (Scheme 61). 120 Thus, pinacolate 79 underwent the C-C coupling with various alkenyl bromides or triflates 124 to generate diene 125, that reacted with another molecule of 79 at elevated temperature (150 °C) to give mixtures of regioisomers 126a and 126b (126a:126b = 1.9:1 to 4.5:1, presumably due to the steric factor). The method was evaluated for other vinyl boronates, which gave lower regioselectivity.…”

Section: Scheme 59 [4+2] Cycloaddition Of Alkenyl Boronates Via O-quimentioning

confidence: 99%

Cycloadditions of Alkenylboronic Derivatives

et al. 2020

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The literature on cycloaddition reactions of boron-containing alkenes is surveyed with 132 references. The data are categorized according to the reaction type ([2+1], [2+2], [3+2], [4+2], and [4+3] cycloadditions). The cyclopropanation and the Diels–Alder reactions of alkenylboronic derivatives have been studied more or less comprehensively, and for some substrates, they can be considered as convenient methods for the rapid regio- and stereoselective construction of even complex cyclic systems. Other types of the cycloadditions, as well as mechanistic aspects of the processes, have been addressed less thoroughly in the previous works.1 Introduction2 [2+1] Cycloaddition2.1 Cyclopropanation2.1.1 With Methylene Synthetic Equivalents2.1.2 With Substituted Carbenoids2.2 Epoxidation2.3 Aziridination3 [2+2] Cycloaddition4 [3+2] Cycloaddition4.1 With Nitrile Oxides4.2 With Diazoalkanes4.3 With Nitrones4.4 With Azomethine Ylides5 [4+2] Cycloaddition6 [4+3] Cycloaddition7 Conclusions and Outlook

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“…48 Scheme 24 Chemoselective cross-coupling of vinyl BPin: Example scope From the synthetic perspective, we realized that if we could achieve this in a reaction containing three different olefins then we might be able to deliver a system that allows selective cross-coupling of vinyl BPin to deliver a diene that would undergo Diels-Alder reaction to give cyclohexenes (Scheme 25). 48,55 Depending on whether the reaction proceeded via Mizoroki-Heck or Suzuki-Miyaura, the cyclohexene product would be borylated or nonborylated, respectively.…”

Section: Account Syn Lettmentioning

confidence: 99%

The Problem with Problems: Fundamental to Applied Research Using Palladium

Watson¹

2020

Synlett

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This Account describes the development of our cross-coupling and medicinal chemistry research from its origins at the outset of my independent career through to the present day. Throughout, the decisions and motivations as well as the mistakes and pitfalls are discussed.1 Introduction2 Hobbies and Interests3 Scooped before Starting4 Opportunity from Collaboration5 Chemoselective Suzuki–Miyaura Cross-Coupling6 Applications to the Medicinal Chemistry Campaign7 Autotaxin and Heterocycle Synthesis8 ATX Hybrids and Pd(II) Speciation9 Conclusions

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A Cascade Suzuki–Miyaura/Diels–Alder Protocol: Exploring the Bifunctional Utility of Vinyl Bpin

Cited by 15 publications

References 36 publications

Ru(0)-Catalyzed Regioselective Synthesis of Borylated-1,4- and -1,5-Diene Building Blocks

Ru(0)-Catalyzed Regioselective Synthesis of Borylated-1,4- and -1,5-Diene Building Blocks

Cycloadditions of Alkenylboronic Derivatives

The Problem with Problems: Fundamental to Applied Research Using Palladium

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