Synthesis and structural revision of naturally occurring ayapin derivatives

The synthesis of three highly oxygenated naturally occurring coumarins, 8-methoxy-6,7-methylenedioxycoumarin, 5-methoxy-6,7-methylenedioxycoumarin and 5,8-dimethoxy-6,7-methylenedioxycoumarin is described for the first time, together with a new method for the preparation of ayapin (6,7-methylenedioxycoumarin). Comparison of the spectroscopic data of the synthetic tetraoxygenated coumarin 5,8-dimethoxy-6,7-methylenedioxycoumarin with literature reports resulted in the structural revision of several natural coumarins. Two coumarins, both identified as 5,8-dimethoxy-6,7-methylenedioxycoumarin must have other structures, while the structure of another coumarin, described as the isomeric 7,8-dimethoxy-5,6-methylenedioxycoumarin has to be revised to 5,8-dimethoxy-6,7-methylenedioxycoumarin.     

Further revisions on the diterpenoid alkaloids reported in a JNP paper (2012, 75, 1145–1159)

We have corrected (Tetrahedron2013, 69, 5859–5866) the structures of diterpenoid alkaloids reported in the Journal of Natural Products2012, 75, 1145–1159. Our follow-up experiments compel us to present further revisions and clarifications on the diterpenoid alkaloids:     

“海水提镁”项目式教学设计与实践*

依托广西北海市丰富的海洋资源,创设了“在北海能否建提镁厂”的驱动性总任务,师生合议将任务规划为3个大问题和6个子任务。学生采用信息收集、分类、比较、推理、实验、系统分析等认知策略,最终以ppt的形式进行成果汇报,通过组间评价、核心问题讨论、决策性问题辩论等方式逐步落实项目目标。     

根据计算结构因子重新指定镍(II)8-羟基喹啉的两个络合物(英文)

晶体学研究曾认为分子式是NaNiQ2HQCLO4的结构并不含有钠而应为H3ONiQCLO4.相似地,稀土-Ni络合物YQHQ2NiQ3CLO4也不含有钇而应为H3ONi2Q3CLO4.晶体结构描述的修正系根据文献报导的原子坐标计算结构因子所导出的结果.     

Exceptions and counterexamples: Understanding Abel's comment on Cauchy's Theorem

It may seem odd that Abel, a protagonist of Cauchy's new rigor, spoke of “exceptions” when he criticized Cauchy's theorem on the continuity of sums of continuous functions. However, when interpreted contextually, exceptions appear as both valid and viable entities in the early 19th century. First, Abel's use of the term “exception” and the role of the exception in his binomial paper is documented and analyzed. Second, it is suggested how Abel may have acquainted himself with the exception and his use of it in a process denoted critical revision is discussed. Finally, an interpretation of Abel's exception is given that identifies it as a representative example of a more general transition in the understanding of mathematical objects that took place during the period. With this interpretation, exceptions find their place in a fundamental transition during the early 19th century from a formal approach to analysis toward a more conceptual one.     

Projective DNF formulae and their revision

Combinatorial and learnability results are proven for projective disjunctive normal forms, a class of DNF expressions introduced by Valiant.     

Synthesis and structural revision of marine eicosanoid agardhilactone

Synthesis of the marine eicosanoid agardhilactone has been achieved. The relative and absolute configuration of agardhilactone was successfully determined.     

Biomimetic total synthesis and structure confirmation of myrtucommulone K

A confirmed structure of meroterpenoid myrtucommulone K, which is vastly different from the originally reported one, is conducted. The first biomimetic total synthesis towards the assignment of its absolute configuration has been efficiently accessed in 5 steps, and key to the success was a heteroatom Diels-Alder cycloaddition. The structure of myrtucommulone K was re-elucidated and confirmed by extensive spectroscopic interpretation of 1D and 2D NMR.     

Synthetic study of a moss-produced oxylipin and its structural revision

The proposed structure for a moss-produced acetylenic oxylipin (10-keto-type structure) was synthesized from a known glycidol derivative by an 11-step sequence involving epoxide ring opening with a terminal acetylene and enzymatic hydrolysis of a methyl ester intermediate. The NMR spectra of the proposed structure was, however, different from those of the natural oxylipin, which prompted us to synthesize its 9-epi-isomer and two diastereomeric 12-keto-type positional isomers. Comparison of the NMR spectra of the three isomers with those of the natural oxylipin indicated that the natural oxylipin was actually a mixture of the two diastereomeric positional isomers.