Regitz Diazo Transfer Reaction for the Synthesis of 1,4,5-Trisubstituted 1,2,3-Triazoles and Subsequent Regiospecific Construction of 1,4-Disubstituted 1,2,3-Triazoles via C-C Bond Cleavage.

A straightforward and efficient methodology has been developed for the synthesis of 1,4,5-trisubstituted dicarbonyl 1,2,3-triazoles and 1,4-disubstituted sole-carbonyl 1,2,3-triazoles via a C-C bond cleavage process. The Regitz diazo transfer and C-C bond cleavage were the key steps of this transformation, which provided diverse carbonyl-substituted structural 1,2,3-triazoles. This reaction featured with excellent regioselectivity, wide functional group tolerance, and mild conditions.

[Analysis the syndrome differentiation of sepsis by the theories of "four patterns and four methods" under the guidance of "ministerial fire theory"].

OBJECTIVE: At present, the main use of Chinese medicine in the treatment of sepsis and sepsis shock is "four patterns and four methods". Although this method is suitable for clinical treatment, it is difficult for doctors to use, and the relationship between "four patterns" has not been clarified. The author introduces the dialectical thinking of "ministerial fire theory", and aims to interpret "four patterns and four methods". Sepsis and sepsis shock can be devided into four stages: Yang excess, Yin insufficient, fire damage, and fire decay, which corresponding to four disease stages: heat syndrome, heat syncope, cold syncope, and decaying, and the corresponding treatments are heat clearing, nourishing Yin, rescue Yang, rescue shock respectively. Abdominal problems should be considered during this process.

[Brief analysis on The Latest Practicing Western Acupuncture].

The Latest Practicing Western Acupuncture, a book of acupuncture translated from Japanese version, The Practicing Acupuncture Collections, is considered as the earliest acupuncture book that introduced anatomy into acupoints in modern times of China. What the book said are very abundant, which mainly about the history of acupuncture, anatomy of the acupoints, acupuncture treatment, and case report. The Latest Practicing Western Acupuncture was compiled and published by the scientific acupuncture tide that time; western knowledge are very rich in content, introducing anatomy into acupoints depiction, which is one of distinctive characteristics. Western medical names of disease are also employed by this book, that inspired so much for traditional acupuncture innovation of China. This article outlines the book's profile, compiler's information, the main contents of each chapter, and takes a brief discussion on the book's content characteristics and the influence on acupuncture of China later.

Silver-catalyzed decarboxylative acylation of quinoxalin-2(1H)-ones with α-oxo-carboxylic acids.

A novel silver-catalyzed decarboxylative acylation of α-oxo-carboxylic acids was developed, by which various 3-acyl quinoxalin-2(1H)-ones were synthesized by direct C-H bond acylation of quinoxalin-2(1H)-ones. In this method, α-oxo-carboxylic acids served as efficient acylating reagents to in situ generate the required active acyl radical. Its excellent chemoselectivity allowed the molecular diversity of 3-acyl quinoxalin-2(1H)-ones to be achieved by convenient functionalizations of both N1- and C3-positions.

Tandem Synthesis of α-Diazoketones from 1,3-Diketones.

A highly efficient synthesis of α-diazoketone was achieved by simply stirring the mixture of 1,3-diketone, TsN3, and MeNH2 in EtOH. It was a tandem reaction including a novel primary amine-catalyzed Regitz diazo transfer of 1,3-diketone and a novel primary amine-mediated C-C bond cleavage of 2-diazo-1,3-diketone.

In-situ Generated and Premade 1-Copper(I) Alkynes in Cycloadditions.

The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) was discovered in 2002, which has become the most remarkable example for "click chemistry" to date. In CuAAC reaction, 1-copper(I) alkyne has been recognized to be a key intermediate. However, many contradictory experimental results for this intermediate were reported in literature. For example, only the in-situ generated 1-copper(I) alkyne was used, while the premade 1-copper(I) alkyne proved to be inefficient under the standard conditions. The kinetic studies indicated that CuAAC reaction had a strict second-order dependence on Cu(I) and the DFT studies demonstrated that 1-copper(I) alkyne intermediate should be a dinuclear copper(I) complex. But these results were inconsistent with the structure of the premade 1-copper(I) alkyne. Although hundreds of structurally different ligands were reported to significantly enhance the efficiency of CuAAC reaction, their functions were assigned to prevent the oxidation and the disproportionation of Cu(I) ion. Based on the investigation of the references and our works, we proposed that the in-situ generated 1-copper(I) alkyne in CuAAC reaction is not identical with the premade 1-copper(I) alkyne. The ligands may play dual roles to activate the 1-copper(I) alkyne by blocking the polymerization of the in-situ formed 1-copper(I) alkynes and dissociating the polymeric structures of the premade 1-copper(I) alkynes. As a result, we first disclosed that carboxylic acids can function as such activators and a novel carboxylic acid-catalyzed CuAAC strategy was developed, which has been proven to be the most convenient and highly efficient CuAAC method to date. Furthermore, highly efficient and regioselective methods for the syntheses of 1,4,5-trisubstituted 1,2,3-triazoles were developed by using the premade 1-copper(I) alkynes as substrates, in which the novel function of the premade 1-copper(I) alkynes as excellent dipolarophiles was first disclosed and applied. In this article, a series of works reported by our group for the in-situ generated and the premade 1-copper(I) alkynes in cycloadditions are reviewed.

[Classification and characteristic of the acupuncture medical literature during the period of the Republic of China].

The acupuncture medical literature during the Republic of China is divided into four categories, including theoretical literature, acupuncture channels and acupoints drawing literature, translations, and teaching materials and medical cases. It is found that the theoretical literature focuses on inheriting the traditional theories as well as combining traditional Chinese and Western medicine. The drawings are becoming more and more precise, and in these drawing works anatomy begins to appear at that time. Translations are the achievements of communication between TCM and Western medicine, which promote the scientization of acupuncture greatly. Teaching materials are also influenced by Western medicine, presenting a rough frame of modern acupuncture disciplinary system. As important clinic data, medical cases have great clinical value. Overall, acupuncture medical literature during the Republic of China is widely published, which is influenced greatly by the Western medicine and presents a significant tendency of scientization.

Tandem Synthesis of 3-chloro-4-iodoisoxazoles from 1-copper(I) alkynes, dichloroformaldoxime, and molecular iodine.

A tandem synthesis for structurally novel 3-chloro-4-iodoisoxazoles was developed by simply mixing 1-copper(I) alkynes, dichloroformaldoxime, and molecular iodine together. The combination of 1-copper(I) alkyne and molecular iodine was well used as a synthetic equivalent of 1-iodoalkyne without the need for tedious preparation, purification, and storage of 1-iodoalkyne.

Tandem reaction of 1-copper(I) alkynes for the synthesis of 1,4,5-trisubstituted 5-chloro-1,2,3-triazoles.

A novel tandem reaction of 1-copper(I) alkynes with azides (cycloaddition) and then NCS (electrophilic substitution) was developed as an efficient method for the synthesis of 1,4,5-trisubstituted 5-chloro-1,2,3-triazoles. The method offers a rare example that a tandem reaction of an organometallic substrate does not involve in the reactivity of the metal-carbon bond in the first step.