Stereoselective Synthesis of Conjugated 2,4-Alkadienoates via the Palladium-Catalyzed Cross-Coupling of 1-Alkenylboronates with 3-Bromo-2-alkenoates

Yanagi, Teiji; Oh-e, Takayuki; Miyaura, Norio; Suzuki, Akira

doi:10.1246/bcsj.62.3892

Cited by 37 publications

(11 citation statements)

References 12 publications

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“…ii. Syntheses of the (2Z,4E) and (2E,4Z) isomers of some conjugated dienes by Negishi (27,35) and Suzuki (32,33,35,41) alkenylations are known. Whereas Negishi coupling has uniformly led to ≥97-98% stereoselectivity, Suzuki reported stereo scrambling to varying extents (≥5%) for the synthesis (18) and used in the subsequent Stille coupling for a total synthesis of (+)-sorangicin A (46).…”

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confidence: 99%

Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation–Pd-catalyzed cross-coupling

Wang

Mohan

Negishi

2011

Proc. Natl. Acad. Sci. U.S.A.

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All four stereoisomers (7-10) of ethyl undeca-2,4-dienoate were prepared in ≥98% isomeric purity by Pd-catalyzed alkenylation (Negishi coupling) using ethyl (E)-and (Z)-β-bromoacrylates. Although the stereoisomeric purity of the 2Z,4E-isomer (8) prepared by Suzuki coupling using conventional alkoxide and carbonate bases was ≤95%, as reported earlier, the use of CsF or n Bu4NF as a promoter base has now been found to give all of 7-10 in ≥98% selectivity. Other widely known methods reveal considerable limitations. Heck alkenylation was satisfactory for the syntheses of the 2E,4E and 2E,4Z isomers of ≥98% purity, but the purity of the 2Z,4E isomer was ≤95%. Mutually complementary HornerWadsworth-Emmons and Still-Gennari (SG) olefinations are also of considerably limited scopes. Neither 2E,4Z nor 2Z,4Z isomer is readily prepared in ≥90% selectivity. In addition to (2Z,4E)-dienoic esters, some (2Z,4E,6E)-and (2Z,4E,6Z)-trienoic esters have been prepared in ≥98% selectivity by a newly devised Pd-catalyzed alkenylation-SG olefination tandem process. As models for conjugated higher oligoenoic esters, all eight stereoisomers for ethyl trideca-2,4,6-trienoate (23-30) have been prepared in ≥98% overall selectivity.highly selective synthesis | Pd-catalyzed Negishi coupling A lkenes represent a large number of natural products of bioactive and medicinally important compounds. Of interest in this study are those containing conjugated dienes and oligoenes (1-11) (Fig. 1). Among numerous known methods for the syntheses of alkenes including conjugated dienes and oligoenes (12, 13), carbonyl olefination reactions, notably Wittig olefination (14) and its variants, such as Horner-Wadsworth-Emmons (HWE hereafter) (15, 16), and Still-Gennari (SG hereafter) (17) as well as Ando (18) modifications have been widely used along with related Si-promoted (Peterson) (19) and S-promoted (Julia and Paris) (20) olefination reactions. As useful as these reactions are, they often lack very high (≥98%) stereoselectivity.In search for highly (≥98%) stereoselective alkene synthesis methodology, our attention was initially drawn to alkyne hydroboration, which generally proceeds in >99% syn-selectivity. Following some promising leads of Brown (21) and Zweifel and co-workers (22-25), we reported in 1973 a couple of highly selective routes to 1,4-disubstituted (E,E)-and (E,Z)-1,3-dienes (1, 3, 26), which appear to represent the earliest syntheses of unsymmetrically substituted conjugated dienes in very high (≥97%) selectivity via organometallic alkenylation.Despite highly selective and satisfactory results described above, our continued search for a more generally applicable and straightforward route to conjugated di-and oligoenes led to the discovery in 1976 of the Pd-catalyzed alkenyl-alkenyl coupling with alkenylalanes (27) and subsequently with alkenyl derivatives containing Zr (28) and Zn (29), collectively known as Negishi coupling (30,31). Along with the subsequently developed alkenylboron version (Suzuki coupling) (32-34), the Pd-catalyzed alken...

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Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation–Pd-catalyzed cross-coupling

Wang

Mohan

Negishi

2011

Proc. Natl. Acad. Sci. U.S.A.

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“…Recent development 17 on the utilization of alkyl- and alkenylboronic acids and esters suggested a convenient method for the preparation of diisopropyl ( Z )-1-decenylboronate ( 12 ). Under standard Suzuki reaction conditions 18 1.0 equiv of 11 and 4.0 equiv of 12 were coupled in the presence of Pd(OAc) 2 , PPh 3 and Na 2 CO 3 in a mixture of solvents (toluene : EtOH : water = 2 : 1 : 1) at refluxing temperature for 6h. Compound 13 was obtained stereo-selectively in an excellent yield.…”

Section: Resultsmentioning

confidence: 99%

Regio- and Stereoselective Syntheses of the Natural Product CCR5 Antagonist Anibamine and its Three Olefin Isomers

et al. 2011

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The syntheses of the natural product anibamine and its three olefin isomers have been achieved concisely and efficiently via highly regio- and stereo-selective reactions. The crucial steps included a regio-selective palladium-catalyzed alkynylation by Sonogashira coupling and a stereo-selective Suzuki coupling. Further conformation analyses and in vitro calcium mobilization studies were carried out to characterize the compounds' biological properties.

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Section: Negishi-kupplungunclassified

“…Die Kreuzkupplung hat sich überwiegend in den letzten vierzig Jahren zu einer der vielseitigsten Methoden für C-C-Verknüpfungen entwickelt. Im Zentrum dieser Forschungen steht die Pd-katalysierte Kreuzkupplung mit Organometallderivaten von Al, Zn, Zr (Negishi-Kupplung), [2,3] B (Suzuki-Kupplung) [2,4] und Sn (Stille-Kupplung) [2,5] sowie von mehreren anderen Metallen wie Cu, [6] In, [7] Mg, [8] Mn [9] und Si [10] (Hiyama-Kupplung). Trotz ihres deutlich kleineren Anwendungsbereichs hat die von Tamao und Kumada [11a,b] sowie von Corriu [11c] beschriebene Ni-katalysierte Grignard-Kreuz-…”

Section: Entwicklung Der Pd-katalysierten Kreuzkupplungunclassified

“…Dieser duale Charakter macht B zu einem interessanten Metall in der Pd-katalysierten Kreuzkupplung. [4] Pd als optimale Katalysatorkomponente Auch wenn sich Cu, [25] Ni, [11,15,26,27] Fe [28] und einige andere d-Block-Übergangsmetalle als nützliche Elemente in der C-C-Kreuzkupplung erwiesen haben, ist Pd derzeit der weitaus nützlichste Katalysator in der katalytischen Kreuzkupplung. Kurz gesagt: Es hat wie andere Übergangsmetalle einige Eigenschaften von entscheidender Bedeutung, darunter die Fähigkeit zu rascher Wechselwirkung mit unpolaren p-Bindungen wie in Alkenen, Alkinen und Arenen, die, wie in Schema 3 gezeigt, zu leichter, selektiver und oft reversibler oxidativer Addition, Transmetallierung und reduktiver Eliminierung führt.…”

Section: Verwendung Von Metallen Mittlerer Elektronegativität Am Beisunclassified

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Die magische Kraft der Übergangsmetalle: Vergangenheit, Gegenwart und Zukunft (Nobel‐Aufsatz)

Negishi

2011

Angewandte Chemie

184

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In meinem ersten Jahr an der Shonan errang damit den 123. Platz der schulischen Leistung unter etwas mehr als 400 Mitschülern. Nach einem kurzen Augenblick der Enttäu-schung erkannte ich, dass zwar etwas mehr als 100 Schüler vor mir lagen, aber auch fast 300 hinter mir. Damals wurden jährlich etwa 30-40 Schüler von Shonan einschließlich der einmaligen Wiederholer an der Universität Tokio aufgenommen. Mir wurde dann plötzlich klar, dass ich sogar eine berechtigte Chance hätte, an die bis dahin für mich unerreichbar scheinende Universität Tokio zu kommen, wenn ich so hart wie möglich lernte.

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Stereoselective Synthesis of Conjugated 2,4-Alkadienoates via the Palladium-Catalyzed Cross-Coupling of 1-Alkenylboronates with 3-Bromo-2-alkenoates

Cited by 37 publications

References 12 publications

Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation–Pd-catalyzed cross-coupling

Highly selective synthesis of conjugated dienoic and trienoic esters via alkyne elementometalation–Pd-catalyzed cross-coupling

Regio- and Stereoselective Syntheses of the Natural Product CCR5 Antagonist Anibamine and its Three Olefin Isomers

Die magische Kraft der Übergangsmetalle: Vergangenheit, Gegenwart und Zukunft (Nobel‐Aufsatz)

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