(E)-α-Substituted γ-Alkoxyallylboronic Esters as New Reagents:  Synthesis and Reactivity toward Aldehydes

• Published in: Journal of organic chemistry Vol. 72; no. 3; pp. 984 - 989
• Main Authors: Possémé, Françoise, Deligny, Michael, Carreaux, François, Carboni, Bertrand
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 02.02.2007; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Exact sciences and technology; Organic chemistry; Physical Sciences; Science & Technology; ALCOHOLS; ROUTE; GENERAL-SYNTHESIS; HYDROBORATION; ALKYL; ALLYLBORATION; ACETALS; STEREOSELECTIVE-SYNTHESIS; DIASTEREOSELECTIVE ADDITION; 3-COMPONENT; Stereoselectivity; Ester; Diol; Purification; Organometallic compound; Allylic rearrangement; Boron Organic compounds; Aldehyde; Chemical reactivity; Chemical synthesis; Diastereoselectivity; Anti stereoisomer
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0622330

We have developed a synthesis of new allylboration reagents based on an allylic rearrangement. This approach led to the α-substituted γ-alkoxyallylboronates 2 with a high stereoselectivity in favor of the E-isomer, independent of the organometallic used. We have also studied the reactivity of these reagents toward aldehydes, showing that the allylboration reaction occurs with an excellent diastereoselectivity to give the anti-diol derivatives 5. Moreover, the sequence can be carried out in a “one-pot” procedure avoiding the purification of allylboronates.