First Total Synthesis and Stereochemical Definition of Isodomoic Acid G

Ni, Yi; Amarasinghe, Kande K. D.; Ksebati, Bashar; Montgomery, John

doi:10.1021/ol0355783

Cited by 64 publications

(20 citation statements)

References 19 publications

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“…The nickel-catalyzed cyclization of alkyne 85 with the vinyl zirconium reagent 84 derived from alkyne 83 was used to prepare directly the isodomoic acid G core structure. [61] Notably, the pyrrolidine unit, the C2/C3 relative stereochemistry, and the complete densely functionalized 1,3-diene were assembled in a single operation in a completely selective fashion to allow an efficient total synthesis of this natural product.…”

Section: Nickel-catalyzed Couplingsmentioning

confidence: 99%

Nickel‐Catalyzed Reductive Cyclizations and Couplings

2004

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For over 50 years, nickel catalysis has been applied in cycloaddition processes. Nickel-catalyzed reductive couplings and cyclizations, however, have only recently attracted a high level of interest. This group of new reactions allows a broad range of multicomponent couplings involving two or more pi components with a main-group or transition-metal reagent. These processes allow the assembly of important organic substructures from widely available reaction components. Multiple contiguous stereocenters, polycyclic ring systems, and novel arrays of complex functionality may often be prepared from simple, achiral, acyclic precursors. With three or more reactive functional groups participating in the catalytic processes, many mechanistic questions abound, including the precise timing of bond constructions and the nature of reactive intermediates. This Review is thus aimed at providing a critical evaluation of recent progress in this rapidly developing field.

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Section: Nickel-catalyzed Couplingsmentioning

confidence: 99%

Nickel‐Catalyzed Reductive Cyclizations and Couplings

2004

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“…A more complex member of the kainoid amino acid class of natural products is isodomoic acid G. This structure lacks the C 4 stereocenter but instead possesses an exocyclic tetrasubstituted alkene. The core structure was constructed in a single step by nickel -catalyzed cyclization of 10 with the vinylzirconium alkylating reagent 11 in 74% yield (Scheme 8.12 ) [34] . Notably, the pyrrolidine fi ve -membered ring, C 2 /C 3 relative stereochemistry, and 1,3 -diene motif were assembled in a completely stereoselective fashion in a single operation.…”

Section: Use In Natural Product Synthesismentioning

confidence: 99%

Nickel‐Catalyzed Reductive Couplings and Cyclizations

Malik

Baxter

Montgomery

2010

Catalysis Without Precious Metals

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Many classes of standard organic transformations involve the coupling or cycloaddition of two different π -components to assemble a more functionalized product. Many such processes are amenable to the union of two complex fragments, thus allowing convergent approaches to complex organic molecules. Diels -Alder cycloadditions, Prins addition reactions, and ene reactions are examples of broadly useful processes that involve the union of two π -components in a selective manner. As a complement to these classical transformations, the reductive coupling of two π -components provides an alternative strategy for assembly of complex fragments from the same types of starting materials [1 -8] . Whereas the starting components resemble those required for the types of standard organic transformations noted above, the products obtained differ structurally and are obtained in a reduced oxidation state based on the action of the reducing agent employed.A number of transition metal catalyst/reducing agent combinations are known to promote various reductive coupling processes. In addition to the nickelcatalyzed variants that are the subject of this chapter, important advances have been made with titanium -[9 -13] , iridium - [14] , and rhodium -catalyzed variants [15] . Many reducing agents have been employed, and the most widely used classes include silanes, organozincs, organoboranes, molecular hydrogen, and alcohols. The specifi c focus of this chapter will be the development of nickel -catalyzed reductive couplings and cyclizations between a polar π -component and a non -polar π -component. This strategy allows the two π -components to be differentiated in catalytic reactions, and thus avoids homocoupling processes that are often problematic in transformations of this type. The use of either aldehydes or α , β -unsaturated carbonyls as the polar component, and alkynes as the non -polar component has been a primary focus of our laboratories and will be the subject of this chapter. Extensive related developments involving dienes as the non -polar component reported by the laboratories of Mori [16] , Sato [17] , and Tamaru [18] have been reviewed elsewhere [3] and will not be extensively discussed in this 8 Catalysis Without Precious Metals. Edited by R. Morris Bullock

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“…The nickel-mediated reaction was used as a strategy for the total synthesis of natural products, a-alokainic acid [77,78] and isodomoic acid G [79], and the synthesis of isogeissoschizine skeleton (Scheme 4.32) [80].…”

Section: Sequential Reaction With Enonesmentioning

confidence: 99%

Reaction of Alkynes

Ikeda

2005

Modern Organonickel Chemistry

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Since the earliest investigations represented by cycloaddition [1] and carboxylation [2], the nickel-catalyzed reactions of alkynes have been extensively studied by many research groups. This chapter highlights recent developments in the nickelcatalyzed reactions of alkynes. Recent advancements in cycloaddition and the carboxylation of alkynes are described in Chapters 6 and 7, respectively.The most extensively studied reaction is the addition reaction of an AaB species (e.g., HaH, H-metals, metals-metals, CaH, and C-metals, where metals ¼ Si, Sn, B, etc.) to alkynes (Scheme 4.1). Generally, the addition of an AaB species to alkynes starts with oxidative addition of the AaB species to a nickel(0) complex to generate an AaNiaB species (see Section 1.7.1). The insertion of an alkyne into either the AaNi or the BaNi bond gives the alkenylnickel intermediate(s), which undergo reductive elimination to produce the alkenes functionalized with an A and B functionalities at the 1,2-positions (see Section 1.7.4). The A and B groups are usually introduced on the same face of alkynes, and cis-alkenes with respect to A and B are produced. When an AaB is CaX (X ¼ halogens, O, N), the alkenylnickel X intermediates are capable of undergoing, instead of reductive elimination, Modern Organonickel Chemistry. Edited by Y. Tamaru

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First Total Synthesis and Stereochemical Definition of Isodomoic Acid G

Cited by 64 publications

References 19 publications

Nickel‐Catalyzed Reductive Cyclizations and Couplings

Nickel‐Catalyzed Reductive Cyclizations and Couplings

Nickel‐Catalyzed Reductive Couplings and Cyclizations

Reaction of Alkynes

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