A Facile CAN-Mediated Synthesis of Selenocyanates from Arylalkenes and Heteroarenes

Nair, Vijay; Augustine, Anu; George, Tesmol G.

doi:10.1002/1099-0690(200207)2002:14<2363::aid-ejoc2363>3.0.co;2-7

Cited by 44 publications

(20 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Very recently, we have observed similar CAN mediated addition of selenocyanate to styrenes. 9 In view of the success of these reactions and in the context of our recent observation of a very efficient azidoiodination, 10 we attempted the CAN mediated addition of sulfinate and iodide to alkenes with the anticipation that the reaction would lead to iodosulfones efficiently and the latter can serve as excellent precursors for vinyl sulfones. The reaction, however, proceeded to afford vinyl sulfones directly; a preliminary report of this work has been published.…”

mentioning

confidence: 99%

CAN Mediated Reaction of Aryl Sulfinates with Alkenes and Alkynes: Synthesis of Vinyl Sulfones, β-Iodovinyl Sulfones and Acetylenic Sulfones

Nair¹,

Augustine²,

Suja³

2002

Synthesis

Self Cite

View full text Add to dashboard Cite

Cerium(IV) ammonium nitrate (CAN) mediated reaction of aryl sulfinates and sodium iodide with alkenes afforded vinyl sulfones in very good yields. Alkynes underwent similar reaction to give b-iodovinyl sulfones, which on treatment with potassium carbonate afforded the corresponding acetylenic sulfones in high yields.Although cerium(IV) ammonium nitrate(CAN) has found much use in carbon-carbon bond forming reactions 1,2 the use of this reagent in carbon-heteroatom bond formation has not been studied extensively. The first report on CAN mediated carbon-heteroatom bond formation was by Trahanovsky who in 1971 observed the addition of azide to alkenes resulting in azidonitrates. 3 This reaction has been subsequently exploited in the synthesis of azidosugars which are key intermediates for aminosugars, by Lemieux et al. 4 Recently we have reported a facile CAN mediated addition of thiocyanate to styrenes 5 and indoles. 6 We have also reported the synthesis of azidocinnamates, 7 phenacylazides and phenacylthiocyanates 8 from the corresponding cinnamates and styrenes respectively. Very recently, we have observed similar CAN mediated addition of selenocyanate to styrenes. 9 In view of the success of these reactions and in the context of our recent observation of a very efficient azidoiodination, 10 we attempted the CAN mediated addition of sulfinate and iodide to alkenes with the anticipation that the reaction would lead to iodosulfones efficiently and the latter can serve as excellent precursors for vinyl sulfones. The reaction, however, proceeded to afford vinyl sulfones directly; a preliminary report of this work has been published. 11 It is noteworthy that the available methodology for vinyl sulfone synthesis mainly consists of the Horner-Emmons 12 reaction of carbonyl compounds and sulfonyl phosphoranes, the Peterson reaction, 13 and b-elimination of selenosulfones 14 or halosulfones. 15 In view of the importance of vinyl sulfones 16 as versatile intermediates in organic synthesis, the known limitations of the existing methods, and the novelty of the present work it was of interest to examine the viability of CAN mediated addition of sulfinate and iodide to alkenes as a convenient alternative to conventional vinyl sulfone syntheses. We have carried out a detailed investigation in this area and the results are presented here.As previously reported, 11 our initial experiments involved the reaction of styrene, sodium p-toluenesulfinate, and sodium iodide in anhydrous acetonitrile with a solution of CAN in the same solvent under a deoxygenated atmosphere. A facile reaction occurred, but instead of the expected b-iodo sulfone, the vinyl sulfone 2a was formed in 82% yield (Scheme 1).Scheme 1 i. p-TolSO 2 Na, NaI, CAN, anhyd CH 3 CN, argon, r.t., 45 min.Impressed by the efficiency of the reaction, we extended it to a number of styrenes. The reaction was found to be general and the results are summarized in Table 1. b-Methylstyrene also showed similar reactivity as shown in Scheme 2. Scheme 2 i. RSO 2 Na, NaI, CAN, anhyd...

show abstract

mentioning

confidence: 99%

CAN Mediated Reaction of Aryl Sulfinates with Alkenes and Alkynes: Synthesis of Vinyl Sulfones, β-Iodovinyl Sulfones and Acetylenic Sulfones

Nair¹,

Augustine²,

Suja³

2002

Synthesis

Self Cite

View full text Add to dashboard Cite

show abstract

“…Drawing inspiration from this work, Nair and co-workers disclosed the usefulness of KSeCN as the selenocyano source in the direct C-H selenocyanation of (hetero)arenes, 24 when indoles 3 underwent regioselective selenocyanation at the C3 position with KSeCN in the presence of 2.3 equiv. of cerium(IV) ammonium nitrate ((NH 4 ) 2 Ce(NO 3 ) 6 ) as a mediator in MeOH to form corresponding 3-(selenocyanato)indoles 4 in high yields (Scheme 2).…”

Section: Metal-catalyzed/mediated Reactionsmentioning

confidence: 99%

Progress and recent trends in the direct selenocyanation of (hetero)aromatic C–H bonds

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Due to these reasons organic selenocyanates and thiocyanates are important precursors and potential targets for synthetic chemists. There are only a few methods available for selenocyanation of aromatic compounds using SeO 2 /malononitrile or CAN/KSeCN systems. Whereas, there are numerous methods available for thiocyanation of aromatic system which employ a variety of reagents such as oxone, aq HIO 5 , IBX,DDQ, I 2 photocatalysts and K 2 S 2 O 8 .…”

Section: Figurementioning

confidence: 99%

N‐Iodosuccinimide Catalyzed Oxidative Selenocyanation and Thiocyanation of Electron Rich Arenes

2016

View full text Add to dashboard Cite

Selenocyanation and thiocyanation of electron rich arenes have been achieved using N‐iodosuccinimide (NIS) as a catalyst and aq. tert‐butyl hydroperoxide (TBHP) as an oxidant at room temperature. This method works efficiently for indoles, anilines, phenols, and other electron‐rich arene systems to furnish the products in good to excellent yields and exhibits a good regioselectivity. The products synthesized are further used to prepare their corresponding trifluoromethyl derivatives using reported reactions.

show abstract

A Facile CAN-Mediated Synthesis of Selenocyanates from Arylalkenes and Heteroarenes

Abstract: Selenocyanation of styrenes and indoles mediated by cerium(IV) ammonium nitrate (CAN) afforded the corresponding selenocyanates in moderate to good yields. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Cited by 44 publications

References 4 publications

CAN Mediated Reaction of Aryl Sulfinates with Alkenes and Alkynes: Synthesis of Vinyl Sulfones, β-Iodovinyl Sulfones and Acetylenic Sulfones

CAN Mediated Reaction of Aryl Sulfinates with Alkenes and Alkynes: Synthesis of Vinyl Sulfones, β-Iodovinyl Sulfones and Acetylenic Sulfones

Progress and recent trends in the direct selenocyanation of (hetero)aromatic C–H bonds

N‐Iodosuccinimide Catalyzed Oxidative Selenocyanation and Thiocyanation of Electron Rich Arenes

Contact Info

Product

Resources

About