Highly Regio‐ and Stereoselective Synthesis of Multialkylated Olefins through Carbozirconation of Alkynylboronates and Sequential Negishi and Suzuki–Miyaura Coupling Reactions

Nishihara, Yasushi; Okada, Yoshiaki; Jiao, Jiao; Suetsugu, Masato; Lan, Ming Tzu; Kinoshita, M.; Iwasaki, Masayuki; Takagi, Kentaro

doi:10.1002/anie.201103601

Cited by 59 publications

(18 citation statements)

References 60 publications

(34 reference statements)

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“…One‐pot synthesis of stilbenes by dehydrohalogenation–Heck olefination and multi‐component Wittig–Heck reaction was recently accomplished by the present authors d. Cascade reactions involving Suzuki reaction as one of the steps have been reported in the literature, although almost all involve phosphine‐based catalyst systems [2e,36–50]. A few examples of double Suzuki reactions have been reported in which excellent control for two different reagents was achieved .…”

Section: Resultsmentioning

confidence: 97%

1‐(α‐Aminobenzyl)‐2‐naphthol as phosphine‐free ligand for Pd‐catalyzed Suzuki and one‐pot Wittig‐Suzuki reaction

Chaudhary

Bedekar

2012

Applied Organom Chemis

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Air stable and easily accessible, 1-(a-aminobenzyl)-2-naphthols are used as efficient phosphine-free ligands in palladiumcatalyzed Suzuki reaction for a variety of substrates under conventional heating as well as ultrasonic conditions. Multibrominated aromatic substrates were successfully converted to corresponding arylated moieties with good conversion and selectivity. A novel one-pot two-step cascade reaction strategy involving Wittig and Suzuki reactions is developed for efficient synthesis of 4-styryl biphenyls (C 6 -C 2 -C 6 -C 6 unit).

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Section: Resultsmentioning

confidence: 97%

1‐(α‐Aminobenzyl)‐2‐naphthol as phosphine‐free ligand for Pd‐catalyzed Suzuki and one‐pot Wittig‐Suzuki reaction

Chaudhary

Bedekar

2012

Applied Organom Chemis

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“…A series of standard operations (protection of the alcohol as its p -methoxybenzyl (PMB) ether, oxidative cleavage of the alkene, reduction, and bromination) proceeded smoothly and delivered, by way of 16 , 17 , and 18 , bromide 19 in 76% overall yield from 15 . Vinyl boronate-alkyl bromide cross-coupling of 13 and 19 using Nishihara’s modification 26 to the original Fu conditions 27 proceeded smoothly and produced 20 in 82% yield (Figure 4c). Finally, acetal deprotection was, to avoid epimerization at C(12), best carried out with TMSOTf and 2,2′-bipyridine, 28 and this produced aldehyde 10 in 81% yield.…”

Section: Resultsmentioning

confidence: 99%

Evolution of an Efficient and Scalable Nine-Step (Longest Linear Sequence) Synthesis of Zincophorin Methyl Ester

2017

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Due both to their synthetically challenging and stereochemically complex structures and their wide range of often clinically relevant biological activities, non-aromatic polyketide natural products have for decades attracted an enormous amount of attention from synthetic chemists and played an important role in the development of modern asymmetric synthesis. Often, such compounds are not available in quantity from natural sources, rendering analog synthesis and drug development efforts extremely resource-intensive and time-consuming. In this arena, the quest for ever more step-economical and efficient methods and strategies – useful and important goals in their own right – takes on added importance and the most useful syntheses will combine high levels of step-economy with efficiency and scalability. The non-aromatic polyketide natural product zincophorin methyl ester has attracted significant attention from synthetic chemists due primarily to the historically synthetically challenging C(8)–C(12) all-anti stereopentad. While great progress has been made in the development of new methodologies to more directly address this problem and as a result in the development of more highly step-economical syntheses, a synthesis that combines high levels of step economy with high levels of efficiency and scalability has remained elusive. To address this problem, we have devised a new synthesis of zincophorin methyl ester that proceeds in just nine steps in the longest linear sequence and proceeds in 10% overall yield. Additionally, the scalability and practicability of the route have been demonstrated by performing all of the steps on a meaningful scale. This synthesis thus represents by a significant margin the most step-economical, efficient, and practicable synthesis of this stereochemically complex natural product reported to date, and is well suited to facilitate the synthesis of analogs and medicinal chemistry development efforts in a time- and resource-efficient manner.

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“…A consistent extension of this work disclosing the application of the Negishi . This was the first example of a stereo-and regiocontrolled preparation of tetrasubstituted alkene 300 bearing four different homologous unbranched and unfunctionalized alkyl groups [82]. To introduce hydrocarbon moieties other than ethyl, a zirconocene-allylation process was proposed (Scheme 10.100) [82].…”

Section: Intermolecular Reactionsmentioning

confidence: 99%

“…This was the first example of a stereo-and regiocontrolled preparation of tetrasubstituted alkene 300 bearing four different homologous unbranched and unfunctionalized alkyl groups [82]. To introduce hydrocarbon moieties other than ethyl, a zirconocene-allylation process was proposed (Scheme 10.100) [82]. Thus, trimethylsilyl-protected allyl alcohol reacted with the intermediate zirconacyclopropene to expand the metallacycle to zirconacyclopentenes 301 in a regioselective manner with respect to the boron moiety at the α-position.…”

Section: Intermolecular Reactionsmentioning

confidence: 99%

Carbometallation Reactions

Marek

Minko

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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Highly Regio‐ and Stereoselective Synthesis of Multialkylated Olefins through Carbozirconation of Alkynylboronates and Sequential Negishi and Suzuki–Miyaura Coupling Reactions

Cited by 59 publications

References 60 publications

1‐(α‐Aminobenzyl)‐2‐naphthol as phosphine‐free ligand for Pd‐catalyzed Suzuki and one‐pot Wittig‐Suzuki reaction

1‐(α‐Aminobenzyl)‐2‐naphthol as phosphine‐free ligand for Pd‐catalyzed Suzuki and one‐pot Wittig‐Suzuki reaction

Evolution of an Efficient and Scalable Nine-Step (Longest Linear Sequence) Synthesis of Zincophorin Methyl Ester

Carbometallation Reactions

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