A convergent approach to the formal total synthesis of hemibrevetoxin B

A convergent synthesis of the key synthetic intermediate of hemibrevetoxin B was achieved via the intramolecular allylation of an α-chloroacetoxy ether and subsequent ring-closing metathesis.     

Formal total synthesis of hemibrevetoxin B by a convergent strategy

Concise construction of the trans-fused 7/7/6/6 tetracyclic ether part of hemibrevetoxin B (1) was achieved by a convergent strategy based on coupling reaction of an acyl anion equivalent, reductive cyclization of an α,ε-dihydroxyketone, and introduction of a methyl group at the central ring junction by the Nicolaou method. The resultant tetracyclic ether was transformed into the known intermediate, which was already converted to 1 by the Yamamoto group, thereby completing the formal total synthesis of 1.     

Convergent synthesis of the ABCDE ring fragment of ciguatoxins

Synthesis of the ABCDE ring fragment of ciguatoxins has been achieved in a highly stereocontrolled and convergent manner via the B-alkyl Suzuki-Miyaura coupling-based approach.     

A new synthesis of key intermediates for the assembly of polycyclic ethers: Yb(OTf)3-promoted formation of O,S-acetals from α-fluorosulfides and alcohols

We report a new reaction for the direct construction of O,S-acetals, key intermediates in the assembly of fused polycyclic ethers. α-Fluorosulfides and secondary alcohols were coupled by the action of Yb(OTf)₃ to generate O,S-acetals in high yield. The neutral and selective nature of the reaction should be useful for synthesizing natural and artificial polyethers with multisensitive functionalities.     

Synthesis of Cryptococcus neoformans Capsular Polysaccharide Structures. Part V: Construction of Glucuronic Acid‐Containing Thioglycoside Donor Blocks

Abstract

Glucuronic acid‐containing di‐ and trisaccharide thioglycoside building blocks, ethyl (benzyl 2,3,4‐tri‐O‐benzyl‐β‐D‐glucopyranosyluronate)‐(1 → 2)‐3‐O‐allyl‐4,6‐di‐O‐benzyl‐1‐thio‐α‐D‐mannopyranoside, ethyl (benzyl 2,3,4‐tri‐O‐benzyl‐β‐D‐glucopyranosyluronate)‐(1 → 2)‐6‐O‐acetyl‐3‐O‐allyl‐4‐O‐benzyl‐1‐thio‐α‐D‐mannopyranoside and ethyl (2,3,4‐tri‐O‐benzyl‐β‐D‐xylopyranosyl)‐(1 → 4)‐[(benzyl 2,3,4‐tri‐O‐benzyl‐β‐D‐glucopyranosyluronate)‐(1 → 2)]‐3‐O‐allyl‐6‐O‐benzyl‐1‐thio‐α‐D‐mannopyranoside, corresponding to repetitive structures in the capsular polysaccharide (CPS) of Cryptococcus neoformans, have been synthesized. The blocks contain an orthogonal allyl group in the 3‐position of the mannose residue to allow formation of the (1 → 3)‐linked mannan backbone of the CPS and benzyl ethers as persistent protecting groups to facilitate access to acetylated target structures. The glucuronic acid moiety was introduced using an acetylated trichloroacetimidate donor and the xylose residue employing the benzoylated bromo sugar to ensure β‐selectivity in the couplings. Exchange to benzyl protecting groups was then performed at the di‐ or trisaccharide level. Assembly of suitable blocks employing DMTST as promoter in diethyl ether then afforded, in high yield and with stereoselectivity, a protected pentasaccharide corresponding to a C. neoformans serotype D CPS structure.     

会聚光在柱状模拟生物组织中的实验研究

在中空的柱状有机玻璃中充入Intralipid-10%溶液构成单层圆柱模拟样品.在会聚单色光入射Intralipid-10%溶液的情况下,利用特制的光纤探头、锁相放大器、斩波器和微动平台等组成测试装置,测量了柱状Intralipid-10%溶液内后向散射光、能流率的空间分布情况,并对测量结果进行分析.对参量不同的溶液中的光分布进行了比较,得出了柱状溶液中光分布的初步规律.     

基于平均和峰值灰度加权的自动调光系统

介绍了在CCD高速电视测量仪系统中,利用电子快门和可变光阑有机结合,在运动控制卡控制下实现自动调光,扩大了调光的动态范围.采用了平均灰度和峰值灰度加权的办法来获取反馈信号,有效的解决不同背景下自调光系统的适应性.提出了基于二次函数的调光反馈量计算方法,提高了调光过程中的收敛速度,同时也保证了系统有较小的超调量.     

A dynamic system model for solving convex nonlinear optimization problems

This paper proposes a feedback neural network model for solving convex nonlinear programming (CNLP) problems. Under the condition that the objective function is convex and all constraint functions are strictly convex or that the objective function is strictly convex and the constraint function is convex, the proposed neural network is proved to be stable in the sense of Lyapunov and globally convergent to an exact optimal solution of the original problem. The validity and transient behavior of the neural network are demonstrated by using some examples.     

Computational experience with the Chow—Yorke algorithm

The Chow—Yorke algorithm is a nonsimplicial homotopy type method for computing Brouwer fixed points that is globally convergent. It is efficient and accurate for fixed point problems. L.T. Watson, T.Y. Li, and C.Y. Wang have adapted the method for zero finding problems, the nonlinear complementarity problem, and nonlinear two-point boundary value problems. Here theoretical justification is given for applying the method to some mathematical programming problems, and computational results are presented.This work was partially supported by NSF Grant MCS 7821337.     

[4 1]及[3 2]会聚式四氢呋喃环合成策略在天然产物全合成中的应用进展

四氢呋喃环广泛存在于具有生物活性的天然产物结构当中,立体选择性地构筑四氢呋喃环往往成为这些天然产物全合成研究中的关键。本文归纳了已有全合成报道中的四氢呋喃环成环策略,以实例展示了其中的会聚式合成策略在近年的发展。相比于直线型的分子内关环策略,以[4+1]、[3+2]为代表的会聚式四氢呋喃关环策略往往能够使全合成的整体路线更加简洁高效,更符合全合成研究领域的发展趋势。