Evolution of multi-component anion relay chemistry (ARC): construction of architecturally complex natural and unnatural products

Abstract

Efficient construction of architecturally complex natural and unnatural products is the hallmark of organic chemistry. Anion Relay Chemistry (ARC) -a multi-component coupling protocol -has the potential to provide the chemist with a powerful synthetic tactic, enabling efficient, rapid elaboration of structurally complex scaffolds in a single operation with precise stereochemical control. The ARC tactic can be subdivided into two main classes, comprising the relay of negative charge either through bonds or through space, the latter with aid of a transfer agent. This review will present the current state of through-space anion relay, in conjunction with examples of natural and unnatural product syntheses that illustrate the utility of this synthetic method

New Mandelalides Expand a Macrolide Series of Mitochondrial Inhibitors

“…Exploiting the reliable Types I and II Anion Relay Chemistry union tactics, 14–16 both the northern [(−)- 12b] and southern [(−) 12c ] hemispheres of 12 were synthesized starting from commercially available and/or readily prepared simple building blocks ( 14–20 ). Union of (−)- 12b and (−)- 12c was achieved by Yamaguchi esterification, 17 to furnish advanced intermediate (−)- 12d in 89% yield.…”

Me3SiSiMe2(OnBu): a disilane reagent for the synthesis of diverse silacycles via Brook- and retro-Brook-type rearrangement

“…The Brook rearrangement enables an intramolecular migration of a silyl group from carbon to oxygen atoms via a hypervalent silicon species, 4 which was initially introduced by Brook 5 and was demonstrated to be a reversible process. 6 Its reverse process, namely retro-Brook rearrangement, can, in turn, be achieved by the transfer of a silyl group from oxygen to carbon atoms ( Scheme 1A ).…”

Carbon‐to‐Carbon Anion Relay Chemistry: Facile Generation of Substituted Allyllithium Species

“…Smith and West have exploited anion relay chemistry (ARC) in which a silicon group migrates from a carbon atom to an oxygen with concomitant generation of a carbanion that can be employed in carbon–carbon bond formation 2. For example, halogen/metal exchange of 3 with tert ‐butyllithium followed by addition of an aldehyde produced 4 .…”