Matsuura Bryan S, Kölle Patrick, Trauner Dirk, de Vivie-Riedle Regina, Meier Robin
Department of Chemistry, Ludwig-Maximilians-Universität , 81377 Munich, Germany.
ACS Cent Sci. 2017 Jan 25;3(1):39-46. doi: 10.1021/acscentsci.6b00293. Epub 2016 Dec 19.
Aplydactone () is a brominated ladderane sesquiterpenoid that was isolated from the sea hare together with the chamigranes dactylone () and 10--dactylone (). Given the habitat of , it seems likely that is formed from through a photochemical [2 + 2] cycloaddition. Here, we disclose a concise synthesis of , , and that was guided by excited state theory and relied on several highly stereoselective transformations. Our experiments and calculations confirm the photochemical origin of and explain why it is formed as the sole isomer. Irradiation of with long wavelength UV light resulted in a [2 + 2] cycloaddition that proceeded with opposite regioselectivity. On the basis of this finding, it seems likely that the resulting regioisomer, termed "8--isoaplydactone", could also be found in .
阿普利达酮()是一种溴化梯形烷倍半萜,它与查米烷类化合物达克托酮()和10--达克托酮()一起从海兔中分离出来。考虑到海兔的栖息地,阿普利达酮似乎是由通过光化学[2 + 2]环加成反应形成的。在此,我们披露了一种以激发态理论为指导并依赖于几种高度立体选择性转化的阿普利达酮、和的简洁合成方法。我们的实验和计算证实了的光化学起源,并解释了它为何作为唯一异构体形成。用长波长紫外光照射会导致[2 + 2]环加成反应,该反应具有相反的区域选择性。基于这一发现,在海兔中也可能找到由此产生的区域异构体,称为“8--异阿普利达酮”。