Synthesis of (±)-7-episordidin

“…Wardrop and coworkers found this to be the case during the synthesis of (±)-7-episordidin, 193 (Scheme 47) [131,132]. The key diazo intermediate en route to the natural product was 190.…”

Section: Scheme 44 Syntheses Of R-(−)-roliprammentioning

confidence: 93%

Functionalization of Carbon–Hydrogen Bonds Through Transition Metal Carbenoid Insertion

Davies

Dick

2009

C-H Activation

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The functionalization of carbon-hydrogen bonds through transition metal carbenoid insertion is becoming a powerful method for the construction of new carbon-carbon bonds in organic synthesis. This chapter will highlight recent developments in this field, while placing it within its historical context. Intramolecular carbenoid C-H insertion will be covered first, focusing on formation of three-and six-membered rings, as well as the use of nontraditional substrates. Additionally, the most recent progress in asymmetric catalysis will be discussed. The bulk of the chapter will concentrate on intermolecular transformations, emphasizing both the effect of substrate structure and the influence of carbene substituent electronics on the regioselectivity of the reactions. Vinyldiazoacetates will be covered as a distinct class of carbenoid precursors, as they have been shown to initiate a variety of unique transformations, such as the combined C-H activation/Cope rearrangement. Finally, the synthetic utility of carbenoid C-H insertion reactions, both intra-and intermolecular, will be displayed through their use in the total syntheses of a number of natural products and pharmaceuticals.

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“…Carbenoids derived from diazoketones are well known for their high reactivity, and, consequently, the development of enantioselective processes for these reagents has been problematic [63,128,145,157] . Signifi cant progress has been made with the introduction of the orthometallated arylphosphine dirhodium(II) complexes.…”

Section: Synthesis Of Carbocyclesmentioning

confidence: 99%