Total Syntheses of Amphidinolides T1 and T4 via Catalytic, Stereoselective, Reductive Macrocyclizations

Colby, Elizabeth A.; O’Brien, Karen C.; Jamison, Timothy F.

doi:10.1021/ja042733f

Cited by 104 publications

(48 citation statements)

References 55 publications

(43 reference statements)

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“…[5] For our synthesis, given in Scheme 2, we should achieve 1) regio-and diastereoselective RCM between C12 and C13 Scheme 1. Structures of amphidinolide T1-T5 (1-5) and the fragments 6 and 7 for total synthesis of amphidinolide T2 (2) by RCM and AD.…”

Section: Dedicated To the Memory Of Professor Xian Huangmentioning

confidence: 99%

A Concise Total Synthesis of Amphidinolide T2

Li¹,

Wu²,

Luo³

et al. 2010

Chemistry A European J

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Section: Dedicated To the Memory Of Professor Xian Huangmentioning

confidence: 99%

A Concise Total Synthesis of Amphidinolide T2

Li¹,

Wu²,

Luo³

et al. 2010

Chemistry A European J

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“…The NHC catalyst is more reactive than analogous phosphinebased catalysts and a broad range of alkynes and aldehydes undergo reductive coupling under these conditions. Macrocyclization via nickel -catalyzed reductive coupling has been shown to be a powerful tool in the synthesis of several natural products, including amphidinolide T1 [41] , amphidinolide T4 [41] , ( − ) -terpestacin [42] , and aigialomycin D [43] . A general protocol for nickel -catalyzed macrocyclizations was published using ligand -based control of regioselectivity (Scheme 8.22 ) [44] .…”

Section: Simple Aldehyde and Alkyne Reductive Couplingsmentioning

confidence: 99%

“…In the synthesis of amphidinolide T1 ( macrocyclization was employed to afford the core natural product structures [41] . Nickel -catalyzed macrocyclization offers a powerful and complementary method to macrolactonization to afford large macrocyclic rings of varying sizes.…”

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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“…Other procedures using TPAP/NMO/PMS/CH 2 Cl 2 include steps in the synthesis of (+)-altholactone (lactol to lactone) [78]; antheliolide A [168]; the AChE inhibitor (+)-arisugacin A and B (primary alcohol to aldehyde step also) [83]; the marine macrolide amphidinolide T1 [169]; the alkaloid (+)-batzelladine D (cf. mech.…”

Section: Natural Product/pharmaceutical Syntheses Involving Secondarymentioning

confidence: 99%

Oxidation of Alcohols, Carbohydrates and Diols

Griffith

2009

Catalysis by Metal Complexes

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This is one of the most important classes of oxidation effected by Ru complexes, particularly by RuO 4 , [RuO 4 ] − , [RuO 4 ] 2− and RuCl 2 (PPh 3 ) 3 , though in fact most Ru oxidants effect these transformations. The chapter covers oxidation of primary alcohols to aldehydes (section 2.1), and to carboxylic acids (2.2), and of secondary alcohols to ketones (2.3). Oxidation of primary and secondary alcohol functionalities in carbohydrates (sugars) is dealt with in section 2.4, then oxidation of diols and polyols to lactones and acids (2.5). Finally there is a short section on miscellaneous alcohol oxidations in section 2.6.In this chapter the first of the two most important categories of oxidations catalysed by Ru complexes (the other being alkene and alkyne oxidations in Chapter 3) are considered. The approach in this and subsequent chapters differs from that of Chapter 1, concentrating here on the substrate rather than on the oxidant. The text is divided into the categories of alcohols and their oxidations. There are summaries in section 2.3.6 of systems of limited applicability which are mentioned only in Chapter 1, and in section 2.3.7 of large-scale (>1 g) oxidations.The first oxidations of alcohols by stoicheiometric RuO 4 /H 2 O were reported in 1958, of primary alcohols to aldehydes or carboxylic acids and secondary alcohols to ketones [1]. The first Ru-catalysed oxidation of an alcohol was reported in 1965 when Parikh and Jones used RuO 2 /aq. Na(IO 4 )/CCl 4 1 ( Table 2.3) [2] to oxidise secondary alcohol groups in carbohydrates.Oxidation of alcohols is the most frequently reviewed topic for Ru-catalysed oxidations [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Mechanisms of alcohol oxidation by Ru complexes have been reviewed [21].

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Total Syntheses of Amphidinolides T1 and T4 via Catalytic, Stereoselective, Reductive Macrocyclizations

Cited by 104 publications

References 55 publications

A Concise Total Synthesis of Amphidinolide T2

A Concise Total Synthesis of Amphidinolide T2

Nickel‐Catalyzed Reductive Couplings and Cyclizations

Oxidation of Alcohols, Carbohydrates and Diols

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