Allylation Reactions of Aldehydes with Allylboronates in Aqueous Media: Unique Reactivity and Selectivity that are Only Observed in the Presence of Water. Issue 9 (17th June 2013)

• Record Type: Journal Article
• Authors: Kobayashi, Shū; Endo, Toshimitsu; Yoshino, Takumi; Schneider, Uwe; Ueno, Masaharu
• Is Part Of: Chemistry, an Asian journal. Volume 8:Issue 9(2013:Sep.)
• Page Start: 2033
• Page End: 2045
• Publication Date: 2013-06-17
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201300440
• Languages: English
• ISSNs: 1861-4728

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Zn(OH)<sub>2</sub>‐catalyzed <named-content id="d402e1923" content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">allylation reactions</named-content> of aldehydes with allylboronates in aqueous media have been developed. In contrast to conventional <named-content id="d402e1926" content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">allylboration</named-content> reactions of aldehydes in organic solvents, the <italic>α</italic>‐addition products were obtained exclusively. A catalytic cycle in which the allylzinc species was generated through a B‐to‐Zn exchange process is proposed and kinetic studies were performed. The key <named-content id="d402e1932" content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">intermediate</named-content>, an allylzinc species, was detected by HRMS (ESI) analysis and by online continuous MS (ESI) analysis. This analysis revealed that, in aqueous media, the allylzinc species competitively reacted with the aldehydes and water. An investigation of the reactivity and selectivity of the allylzinc species by using several typical allylboronates (<bold>6a</bold>, <bold>6b</bold>, <bold>6c</bold>, <bold>6d</bold>) clarified several important roles of water in this <named-content id="d402e1938" content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">allylation reaction</named-content>. The <named-content id="d402e1941" content-type="reactionType" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">allylation reactions</named-content> of aldehydes with allylboronic acid 2, 2‐dimethyl‐1, 3‐propanediol esters proceeded smoothly in the presence of catalytic amounts of Zn(OH)<sub>2</sub> and achiral ligand <bold>4d</bold> in aqueous media to afford the corresponding <italic>syn</italic>‐adducts in high yields with high diastereoselectivities. In all cases, the <italic>α</italic>‐addition products were obtained and a wide substrate scope was tolerated. Furthermore, this reaction was applied to <named-content id="d402e1962" content-type="reactionType chemicalTechnology" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink">asymmetric catalysis</named-content> by using chiral ligand <bold>9</bold>. Based on the X‐ray structure of the Zn‐<bold>9</bold> complex, several nonsymmetrical chiral ligands were also found to be effective. This reaction was further applied to catalytic asymmetric alkylallylation, chloroallylation, and alkoxyallylation processes and the synthetic utility of these reactions has been demonstrated.</p> </abstract>