Metallacycle-mediated cross-coupling in natural product synthesis

O’Rourke, Natasha F.; Kier, Matthew J.; Micalizio, Glenn C.

doi:10.1016/j.tet.2016.08.053

Cited by 22 publications

(11 citation statements)

References 212 publications

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“…Combinations of anionic processes such as conjugate additions with alkylations or aldol reactions have also been used to great effect. Transition-metal-catalysed sequential transformations that result in multiple bond formation have been harnessed in almost every conceivable way [5]. Examples include the Pauson-Khand reaction [6], the powerful metathesis reaction [7], the Heck coupling and numerous related reactions involving palladium complexes [8].…”

Section: Introductionmentioning

confidence: 99%

Some aspects of radical cascade and relay reactions

Quiclet‐Sire¹,

Zard²

2017

Proc. R. Soc. A.

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The ability to create carbon-carbon bonds is at the heart of organic synthesis. Radical processes are particularly apt at creating such bonds, especially in cascade or relay sequences where more than one bond is formed, allowing for a rapid assembly of complex structures. In the present brief overview, examples taken from the authors' laboratory will serve to illustrate the strategic impact of radical-based approaches on synthetic planning. Transformations involving nitrogen-centred radicals, electron transfer from metallic nickel and the reversible degenerative exchange of xanthates will be presented and discussed. The last method has proved to be a particularly powerful tool for the intermolecular creation of carbon-carbon bonds by radical additions even to unactivated alkenes. Various functional groups can be brought into the same molecule in a convergent manner and made to react together in order to further increase the structural complexity. One important benefit of this chemistry is the so-called RAFT/MADIX technology for the manufacture of block copolymers of almost any desired architecture.

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Section: Introductionmentioning

confidence: 99%

Some aspects of radical cascade and relay reactions

Quiclet‐Sire¹,

Zard²

2017

Proc. R. Soc. A.

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“…27). For example, there are several well-established protocols 117,118 for the stepwise addition of alkynes to "Ti II " synthons, resulting in selective formation of titanacyclopentadienes (IM46). Treatment of in situ generated IM46 with TolSO 2 CN results in IM48, either from IM47 or IM47 0 .…”

Section: Pyridinesmentioning

confidence: 99%

Multicomponent syntheses of 5- and 6-membered aromatic heterocycles using group 4–8 transition metal catalysts

et al. 2021

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“…1–5 These reactions that may be considered to be inspired by the foundation of chemistry first established by Reppe, 6 and later developed by luminaries in the field, often embrace organometallic intermediates of relevance for [2+2+2] annulation as a means to realize a large swath of complex and diverse bond-forming reactions. 7–13 While many of these advances have been demonstrated to be of great value in complex molecule or natural product synthesis, 14 it is typically the case that inter molecular versions of this type of organometallic chemistry are rather restricted in scope, and therefore of limited value in stereoselective synthesis, including natural product synthesis. 14 As illustrated in Figure 1B, controlling intermolecular reactivity in metallacycle-mediated coupling chemistry is challenging due to the possibility of generating products of varied composition, in addition to the clear issues of selectivity that surface when employing: (a) unsymmetrical systems (regioselectivity), (b) alkenes as one of the three reactive π-systems (π-facial selectivity), and/or (c) polyunsaturated substrates where issues of chemoselectivity surface.…”

Section: Introductionmentioning

confidence: 99%

A highly chemo-, regio-, and stereoselective metallacycle-mediated annulation between a conjugated enyne and an ene-diyne

Shalit

Micalizio

2018

Arkivoc

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Alkoxide-directed metal-centered intermolecular [2+2+2] annulation is shown to chemo-, regio-, and stereoselectively engage two polyunsaturated substrate in productive cyclization chemistry. This annulation process is unique in the field, revealing that it is possible to selectively engage three of five π-systems residing in the coupling partners in initial [2+2+2] reaction, and demonstrating that one of the two remaining π-systems (the TMS-alkyne) can ultimately serve to simply generate a new metallacyclopentene of great potential value in additional metallacycle-mediated coupling chemistry.

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Metallacycle-mediated cross-coupling in natural product synthesis

Abstract: Graphical abstract

Cited by 22 publications

References 212 publications

Some aspects of radical cascade and relay reactions

Some aspects of radical cascade and relay reactions

Multicomponent syntheses of 5- and 6-membered aromatic heterocycles using group 4–8 transition metal catalysts

A highly chemo-, regio-, and stereoselective metallacycle-mediated annulation between a conjugated enyne and an ene-diyne

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