From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement

Colomer, Ignacio; Velado, Marina; Pradilla, Roberto Fernández de la; Viso, Alma

doi:10.1021/acs.chemrev.7b00428

Cited by 61 publications

(38 citation statements)

References 424 publications

(669 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…3,86−91 In this context, [3,3]- and [2,3]-sigmatropic rearrangements can be instigated by the formation of either unsaturated sulfonium intermediates or allylic sulfoxides and sulfur ylides. 6,7,92−94…”

Section: Sulfoxidesmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

View full text Add to dashboard Cite

Organosulfur compounds have long played a vital role in organic chemistry and in the development of novel chemical structures and architectures. Prominent among these organosulfur compounds are those involving a sulfur(IV) center, which have been the subject of countless investigations over more than a hundred years. In addition to a long list of textbook sulfur-based reactions, there has been a sustained interest in the chemistry of organosulfur(IV) compounds in recent years. Of particular interest within organosulfur chemistry is the ease with which the synthetic chemist can effect a wide range of transformations through either bond formation or bond cleavage at sulfur. This review aims to cover the developments of the past decade in the chemistry of organic sulfur(IV) molecules and provide insight into both the wide range of reactions which critically rely on this versatile element and the diverse scaffolds that can thereby be synthesized.

show abstract

Section: Sulfoxidesmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

View full text Add to dashboard Cite

show abstract

“…[79][80][81][82][83][84][85][86][87][88][89][90] Within the broad landscape of gold catalysis in reaction chemistry, the dexterity of gold catalysis to effect molecular rearrangements will be the main focus of this review. Indeed, increasing the molecular complexity by gold catalyzed rearrangements is quite advantageous over other catalytic methods; [91][92][93][94][95] in terms of scope towards diverse rearrangements, well-understood reactivity pattern, mildness of the process, and excellent selectivities. Although, rearrangement chemistry by gold catalysis has been reviewed in few instances, [97][98][99][100][101][102] the emphasis on regioselectivity has not been covered up to this point.…”

Section: Introductionmentioning

confidence: 99%

Regio‐ and Site‐selective Molecular Rearrangements by Homogeneous Gold Catalysis

Praveen

2020

Asian J Org Chem

View full text Add to dashboard Cite

Homogeneous gold catalysis for connection and disconnection of carbon-carbon (CÀ C) as well as carbonheteroatom (CÀ X) bond constitutes an important zone in molecular chemistry, since all new or existing organic synthesis relies on the transformation of these chemical bonds. Among the diaspora of molecular transformations, rearrangement and shift reactions occupy a special place in organic chemistry, as they enable the synthesis of molecules of increased complexity from simple precursors. However, the rearrangement in substrates possessing more than one potential reaction site produce more than one isomer and could result in regioselective issues. This challenge of selective synthesis of one regisomer over the other was fairly addressed by gold catalysis on various occasions. To this end, the prowess of homogeneous gold catalysis towards regioselective molecular rearrangement reactions and the contributing parameters are comprehensively reviewed. Also, synthetic applicability of regioselective rearrangements by gold catalysis in total and formal synthesis of several natural products was emphasized.This review also covers the emergence of gold catalyzed migratory/shift selective reactions and could be beneficial for synthetic and medicinal chemists.

show abstract

“…1A) 22 . We hypothesized that a dual radical addition / radical coupling strategy might overcome these issues and open up possibilities for the application of sul nyl radicals in organic synthesis, not least by providing a new means to access sulfoxides, which are one of the most important classes of organosulfur compounds [23][24][25] . Speci cally, the coupling of a sul nyl radical with an in situ generated highly reactive carbon-centered radical could suppress the homocoupling of the sul nyl radical, and also avoid generation of a radical at the β-position to the sul nyl group, thus preventing the undesired β-elimination of the sul nyl group.…”

Section: Main Textmentioning

confidence: 99%

Synthetic exploration of sulfinyl radicals using sulfinyl sulfones

Wang

Zhang

Zhao

et al. 2021

Preprint

View full text Add to dashboard Cite

Sulfinyl radicals – one of the fundamental classes of S-centered radicals – have eluded synthetic application in organic chemistry for over 60 years, despite their potential to assemble valuable sulfoxide compounds. Here we report the successful generation and use of sulfinyl radicals in a dual radical addition / radical coupling with unsaturated hydrocarbons, where readily-accessed sulfinyl sulfones serve as the sulfinyl radical precursor. The strategy provides an entry to a variety of previously inaccessible linear and cyclic disulfurized adducts in a single step, and demonstrates excellent tolerance to an extensive range of hydrocarbons and functional groups. Experimental and theoretical mechanistic investigations suggest that these reactions proceed through sequential sulfonyl and sulfinyl radical addition.

show abstract

From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement

Cited by 61 publications

References 424 publications

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Regio‐ and Site‐selective Molecular Rearrangements by Homogeneous Gold Catalysis

Synthetic exploration of sulfinyl radicals using sulfinyl sulfones

Contact Info

Product

Resources

About