Se‐Phenyl Prop‐2‐eneselenoate: An Ethylene Equivalent for Diels–Alder Reactions

Abstract

Upon further examination of the NMR spectra for the products of the reduction of the Se-phenyl 1-methoxybicyclo[2.2.2]oct-5-ene-2-carboselenoate 5 f the authors of this Communication have found that the reaction did not give the expected 1-methoxy-bicyclo-[2.2.2]oct-2-ene 6 f in 67 % yield as reported in Table 1 (entry f). Instead, three major products were obtained in a combined yield of 67 %: the expected product 6 f (16 %) along with the two products of cyclopropylcarbinyl radical rearrangement, the endo (major, 57 %) and the exo (minor, 27 %) isomers of 2-methoxybicyclo[3.2.1]oct-6-ene, the former being a known compound. [1] [1] a) M. A. Battiste, J. M. Coxon, A.

Asymmetric Total Synthesis of Brasilicardins

“…[6][7][8][9] However,t heir complex and unique three-dimensional structure has hampered their chemical synthesis.D espite considerable synthetic efforts over the last twenty years,t he sole successful total synthesis was the de novo construction of 1 and 3 by Anada, Hashimoto,a nd co-workers in 2017, [10] which involved sequential functionalization of the Wieland-Miescher ketone derivative and aD iels-Alder reaction/reductive angular methylation sequence [7] (Scheme 1a). [6][7][8][9] However,t heir complex and unique three-dimensional structure has hampered their chemical synthesis.D espite considerable synthetic efforts over the last twenty years,t he sole successful total synthesis was the de novo construction of 1 and 3 by Anada, Hashimoto,a nd co-workers in 2017, [10] which involved sequential functionalization of the Wieland-Miescher ketone derivative and aD iels-Alder reaction/reductive angular methylation sequence [7] (Scheme 1a).…”

High-Quality Draft Genome Sequence of the Actinobacterium Nocardia terpenica IFM 0406, Producer of the Immunosuppressant Brasilicardins, Using Illumina and PacBio Technologies

“…Both of these facts make the fermentative production of brasilicardin A expensive and elaborate. Due to its complex stereochemistry, a total synthesis has not been achieved to date (11–13). Therefore, we want to overcome this hurdle by heterologous expression of the corresponding biosynthetic gene cluster (14) in a nonpathogenic producer strain.…”

The Immunosuppressant Brasilicardin: Determination of the Biosynthetic Gene Cluster in the Heterologous Host Amycolatopsis japonicum

“…However, the development of this promising immunosuppressant as drug for medical use was so far hindered as N. terpenica IFM 0406 shows only a low production titer and is furthermore categorized as a biosafety‐level 2 organism. Besides, due to its complex stereochemistry total synthesis of brasilicardins could not be achieved; especially the synthesis of the anti‐syn‐anti‐perhydrophenanthrene skeleton made the synthesis of brasilicardin congeners to a yet unsolved task.…”