Departamento de Química Orgánica, Universidad de Valencia, Avenida Vicent Andrés Estellés s/n, 46100, Burjassot, Spain.
Laboratorio de Moléculas Orgánicas, Centro de Investigación "Príncipe Felipe", 46012, Valencia, Spain.
Chem Rec. 2016 Aug;16(4):2046-60. doi: 10.1002/tcr.201600069. Epub 2016 Jun 30.
Asymmetric allylboration has played a central role in organic synthesis ever since the pioneering work by Hoffman and Brown, having found applications in the total synthesis of many natural products. A new dawn for this 40 year-old reaction occurred with the beginning of the new century when the first catalytic asymmetric methods came into play. In less than one decade, several methodologies, able to achieve the desired homoallylic alcohols with ee ranges in the high 90s, were developed. Among them, in the present account, we will disclose our contribution to the development of the chiral binolphosphoric-derived Brønsted acid-catalyzed allylboration of aldehydes originally reported by Antilla in 2010. Our contribution to this field lies in its application to polyfunctionalized systems, both on the aldehyde and the allylboronate in question, which enables the rapid construction of molecular diversity and complexity. Parts of the work described herein have been carried out in collaboration with the groups of Profs. Akiyama and Houk.
不对称烯丙基化反应自 Hoffman 和 Brown 的开创性工作以来一直是有机合成的核心，在许多天然产物的全合成中得到了应用。随着新世纪的到来，第一种催化不对称方法的出现，这种 40 岁的反应迎来了新的曙光。在不到十年的时间里，开发出了几种能够以高达 90%的对映选择性获得所需的同烯丙醇的方法。在这些方法中，我们将在本文中披露我们对 Antilla 于 2010 年首次报道的手性联萘衍生的 Brønsted 酸催化醛的烯丙基化反应的发展所做的贡献。我们在这个领域的贡献在于它在手性联萘衍生的 Brønsted 酸催化醛的烯丙基化反应的发展中的应用，该反应最初由 Antilla 报道，它能够在手性联萘衍生的 Brønsted 酸催化醛的烯丙基化反应中应用于多功能化体系，包括醛和烯丙基硼酸酯，这使得快速构建分子多样性和复杂性成为可能。本文所述的部分工作是与 Akiyama 和 Houk 教授的小组合作完成的。
