A Novel, Highly Selective, and General Methodology for the Synthesis of 1,5-Diene-Containing Oligoisoprenoids of All Possible Geometrical Combinations Exemplified by an Iterative and Convergent Synthesis of Coenzyme Q₁₀

Abstract

[reaction: see text] A truly general, versatile, and highly regio- and stereoselective methodology for the synthesis of terpenoids containing 1,5-diene units of E and/or Z geometry critically involves Pd-catalyzed homoallyl- and homopropargyl-alkenyl coupling and Zr-catalyzed carboalumination of alkynes. By using this methodology, coenzyme Q(10), (E,Z,E)-geranylgeranoil, and other natural or unnatural compounds have been synthesized efficiently.

Highly Stereoselective Synthesis of (1E)‐2‐Methyl‐1,3‐dienes by Palladium‐Catalyzed trans‐Selective Cross‐Coupling of 1,1‐Dibromo‐1‐alkenes with Alkenylzinc Reagents

“…However, it has often been difficult to synthesize trisubstituted alkenes in a highly regioselective manner by hydrometalation of internal alkynes. Carbometalation-based methods, [3,4] on the other hand, have often been shown to be not only highly regio-and stereoselective but also very efficient, as exemplified by recently developed novel, general, and highly selective methods for the synthesis of carotenoids [5] and terpenoids containing 1,5-diene units [6] by involving the Zr-catalyzed carboalumination of terminal alkynes. However, the "head-to-tail" construction [7] of the critical trisubstituted alkene unit has not been a…”

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

“…[17,82,83] 2) Für AlkylAlkyl-Kupplungen ohne Beteiligung benachbarter pBindungen scheint die Reaktion von Alkyl-GrignardReagentien mit Alkylhalogeniden und verwandten Elektrophilen in Gegenwart von Li 2 CuCl 4 oder anderen, ähnlichen Cu-Katalysatoren derzeit die beste Möglich-keit zu sein. [25] Zirconium-katalysierte asymmetrische Carboaluminierung von Alkenen (ZACA-Reaktion) Als wir 1978 die Zr-katalysierte Carboaluminierung von Alkinen (ZMA) entdeckten (Schema 7), [59] kam mir der Gedanke, den Anwendungsbereich dieser Reaktion auf die Alkenvariante für die asymmetrische C-C-Verknüpfung auszudehnen, was einer einstufigen Version der ZieglerNatta-Alkenpolymerisation gleichkommen würde.…”

Transition Metal Catalyzed CarbonCarbon Bond Formation: The Key of Homogeneous Catalysis

“…III ! IV): the Suzuki-Miyaura reaction (Y ¼ B) [8][9][10][11]; the Migita-Kosugi-Stille reaction (Y ¼ Sn) [12][13][14][15]; the Sonogashira coupling reaction (Y ¼ Cu) [7,16,17]; the Kumada-Tamao-Corriu reaction (Y ¼ Mg) [18][19][20]; the Hiyama reaction (Y ¼ Si) [21][22][23][24]; and the Negishi coupling (Y ¼ Zn) [25][26][27]. Other organometallic and heteroatom species, Y ¼ Al, Ge, In, Ag, Te, S, have been also tested as reagents for the transmetallation step [28][29][30][31][32][33][34][35].…”