title: Enantioselective syn and anti Homocrotylation of Aldehydes: Application to the Formal Synthesis of Spongidepsin.
abstract: Whereas crotylboration has been a useful method for synthesis of stereochemically complex products, we have shown that homocrotylboration can be achieved with cyclopropanated crotylation reagents, and that the stereoselectivity of the reaction can be predicted by analogous models. This paper presents a full account of this work, including the first examples of asymmetric anti homocrotylation. The scope of this reaction is demonstrated with highly enantioselective homocrotylation of both aliphatic and aromatic aldehydes, as well as double diastereoselection studies. An application of the synthesis of the marine natural product spongidepsin is presented, as well as streamlined syntheses of homocrotylation reagents.
authors.affiliation: Department of Chemistry, Brandeis University , Waltham, Massachusetts 02454-9110, United States.
authors.forename: Hongkun
authors.initials: H
authors.lastname: Lin
authors.affiliation: Department of Chemistry, Brandeis University , Waltham, Massachusetts 02454-9110, United States.
authors.forename: Leiming
authors.initials: L
authors.lastname: Tian
authors.affiliation: Department of Chemistry, Brandeis University , Waltham, Massachusetts 02454-9110, United States.
authors.forename: Isaac J
authors.initials: IJ
authors.lastname: Krauss
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D047630:Depsipeptides / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D047630:Depsipeptides; C498389:spongidepsin