Switchable Site‐Selective Catalytic Carboxylation of Allylic Alcohols with CO₂

Abstract

A switchable site-selective catalytic carboxylation of allylic alcohols has been developed in which CO is used with dual roles, both facilitating C-OH cleavage and as a C source. This protocol is characterized by its mild reaction conditions, absence of stoichiometric amounts of organometallic reagents, broad scope, and exquisite regiodivergency which can be modulated by the type of ligand employed.

Synthetic fermentation of β-peptide macrocycles by thiadiazole-forming ring-closing reactions

“…Following EDCI/HOBt-mediated coupling with Boc-hydrazine 18 , a Heck reaction between iodide 19 and allyl alcohol ( 20 ) provided aldehyde 21 . 52 An HWE reaction with phosphonate 22 allowed installation of the acetal-protected α-ketoacid framework. 53 , 54 Subsequent conversion to thiohydrazide 24 using Lawesson's reagent, followed by unveiling of the free α-ketoacid via ester hydrolysis afforded initiator 16 .…”

Officer of the Order of the British Empire: P. L. Arnold / Robert T. Koch Gold Medal: C. T. Walsh / Inhoffen Medal: H. Wennemers / OMCOS Award: Rubén Martín

“…Martín was featured here when he won one of the Premios a la Excelencia Investigadora from the Real Sociedad Española de Química (RSEQ; Spanish Royal Society of Chemistry) . He has reported in Angewandte Chemie on the site‐selective catalytic carboxylation of allylic alcohols . Martín is on the International Advisory Board of the European Journal of Organic Chemistry .…”

Officer des Order of the British Empire: P. L. Arnold / Robert‐T.‐Koch‐Goldmedaille: C. T. Walsh / Inhoffen‐Medaille: H. Wennemers / OMCOS Award: Rubén Martín

“…Martín wurde in dieser Rubrik vorgestellt, als er mit einem der Premios a la Excelencia Investigadora der Real Sociedad Española de Química ausgezeichnet worden war . In der Angewandten Chemie hat er die ortsselektive katalytische Carboxylierung allylischer Alkohole beschrieben . Martín ist Mitglied des International Advisory Board des European Journal of Organic Chemistry .…”