The reactions of some α-halo-β-ketosulfones with hard and soft nucleophiles. A preparation of sulfinate esters

The α-halo-β-ketosulfonyl functionality was attacked by ethanethiolate at the halogen which, in the presence of a proton source, usually resulted in reduction to the β-ketosulfone. A range of other soft nucleophiles did not react, whereas hard nucleophiles invariably attacked at the carbonyl, with subsequent cleavage to α-halosulfones. Ambident arylsulfinate anions usually attacked at halogen to form the sulfonyl halide, which reacted with excess sulfinate to give an intermediate that is readily attacked by alcohols. This reaction resulted in the formation of alkyl arylsulfinate esters in reasonable yields. The same reaction occurred when sulfonyl chlorides were reacted with sulfinate salts and it was rationalized by using HSAB principles. Spectral properties of some sulfinate esters are presented.

Download Full-text

Convenient synthesis of sulfinate esters from sulfonyl chlorides

The Journal of Organic Chemistry ◽

10.1021/jo00388a051 ◽

1987 ◽

Vol 52 (12) ◽

pp. 2598-2602 ◽

Cited By ~ 65

Author(s):

Janice M. Klunder ◽

K. Barry Sharpless

Keyword(s):

Sulfonyl Chlorides ◽

Convenient Synthesis ◽

Sulfinate Esters

Download Full-text

ChemInform Abstract: A Convenient Synthesis of Sulfinate Esters from Sulfonyl Chlorides.

ChemInform ◽

10.1002/chin.198749170 ◽

1987 ◽

Vol 18 (49) ◽

Author(s):

J. M. KLUNDER ◽

K. B. SHARPLESS

Keyword(s):

Sulfonyl Chlorides ◽

Convenient Synthesis ◽

Sulfinate Esters

Download Full-text

The [2,3]-sigmatropic rearrangement of propargylic sulfonates to allenic sulfones and further applications to oxacycles and dihydrofuranones

10.32469/10355/50142 ◽

2015 ◽

Author(s):

◽

Rama Rao Tata

Keyword(s):

Intramolecular Cyclization ◽

Acid Catalysis ◽

Sigmatropic Rearrangement ◽

University Of Missouri ◽

Sulfonyl Chlorides ◽

New Synthesis ◽

Sulfinate Esters ◽

Tandem Cyclization ◽

The University ◽

Silver Fluoride

[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT REQUEST OF AUTHOR.] The scope of [2,3]-sigmatropic rearrangement of propargylic sulfinates to allenic sulfones by silver catalysis was expanded. A series of new propargylic sulfinate esters was generated from a variety of aromatic and heteroaromatic sulfonyl chlorides and their rearrangement to allenic sulfones is reported. In addition, the synthesis of propargylic sulfinate esters containing electron-withdrawing benzenesulfonyl chlorides was optimized and reported. In the course of pursuing a Nazarov cyclization of allenyl vinyl ketones (AVK), we discovered multiple new reactions. Allenyl alcohols underwent an intramolecular cyclization to 2,5-dihydrofurans in the presence of Fetizon's reagent and this process was then optimized using silver fluoride. The methodology was expanded to synthesize higher membered oxacycles also. A tandem cyclization of hydroxypropargylic sulfinate esters to 2,5-hydrofurans was also developed. A new synthesis of a'-hydroxyenones was developed by the oxidation of a-allenyl alcohols with Cr (VI) regents and then extended to synthesize dihydrofuran- 3(2H)-ones by acid catalysis.

Download Full-text

Recent Advances of Sulfonylation Reactions in Water

Current Organic Synthesis ◽

10.2174/1570179417666200316124107 ◽

2020 ◽

Vol 17 (4) ◽

pp. 271-281

Author(s):

Li Wu ◽

Lifen Peng ◽

Zhifang Hu ◽

Yinchun Jiao ◽

Zilong Tang

Keyword(s):

Natural Products ◽

Organic Synthesis ◽

Low Cost ◽

Point Of View ◽

Sulfinic Acid ◽

Sulfonyl Chlorides ◽

Recent Advances ◽

Water As Solvent ◽

Proton Source ◽

Sulfinic Acids

Background: The sulfonyl groups are general structural moieties present in agrochemicals, pharmaceuticals, and natural products. Recently, many efforts have been focused on developing efficient procedures for preparation of organic sulfones. Materials and Methods: Water, a proton source, is considered one of the most ideal and promising solvents in organic synthesis for its easy availability, low cost, nontoxic and nonflammable characteristics. From the green and sustainable point of view, more and more reactions are designed proceeding in water. Objective: The review focuses on recent advances of sulfonylation reactions proceeding in water. Sulfonylation reactions using sodium sulfinates, sulfonyl hydrazides, sulfinic acids, and sulfonyl chlorides as sulfonating agents were introduced in detail. Results and Discussion: In this review, sulfonylation reactions proceeding in water developed in recent four yields were presented. Sulfonylation reactions using water as solvent have attracted more and more attention because water is one of the most ideal and promising solvents in organic synthesis for its facile availability, low cost, nontoxic and nonflammable properties. Conclusion: Numerous sulfonating agents such as sodium sulfinates, sulfonyl hydrazides, sulfinic acid, sulfonyl chlorides and disulfides are efficient for sulfonylation reactions which proceed in water.

Download Full-text

ChemInform Abstract: A Convenient and Highly Diastereoselective Synthesis of Optically Active Sulfinate Esters from Sulfonyl Chlorides under Solid State Conditions.

ChemInform ◽

10.1002/chin.199941028 ◽

2010 ◽

Vol 30 (41) ◽

pp. no-no

Author(s):

Abdolreza Hajipour ◽

Fereshteh Islami

Keyword(s):

Solid State ◽

Optically Active ◽

Diastereoselective Synthesis ◽

Sulfonyl Chlorides ◽

Sulfinate Esters

Download Full-text

Palladium-catalyzed carbonylative transformation of aryl iodides and sulfonyl chlorides: convenient access to thioesters

Organic Chemistry Frontiers ◽

10.1039/d0qo00158a ◽

2020 ◽

Vol 7 (6) ◽

pp. 885-889 ◽

Cited By ~ 2

Author(s):

Xinxin Qi ◽

Zhi-Peng Bao ◽

Xiao-Feng Wu

Keyword(s):

Sulfonyl Chlorides ◽

Aryl Iodides ◽

Palladium Catalyzed ◽

Convenient Access

A palladium-catalyzed carbonylative transformation of aryl iodides and sulfonyl chlorides to thioesters has been studied.

Download Full-text

Model of multicomponent narrow-band periodical non-stationary random signal

Information extraction and processing ◽

10.15407/vidbir2020.48.017 ◽

2020 ◽

Vol 2020 (48) ◽

pp. 17-24

Author(s):

I.M. Javorskyj ◽

◽

R.M. Yuzefovych ◽

P.R. Kurapov ◽

◽

...

Keyword(s):

Time Series ◽

Real Time ◽

Hilbert Transform ◽

Spectral Properties ◽

Narrow Band ◽

Analytic Signal ◽

Random Signal ◽

Hilbert Transformation ◽

The Hilbert Transform

The correlation and spectral properties of a multicomponent narrowband periodical non-stationary random signal (PNRS) and its Hilbert transformation are considered. It is shown that multicomponent narrowband PNRS differ from the monocomponent signal. This difference is caused by correlation of the quadratures for the different carrier harmonics. Such features of the analytic signal must be taken into account when we use the Hilbert transform for the analysis of real time series.

Download Full-text