Capperucci, Antonella

Degl&apos

Mordini, A.

Reginato, Gianna

Ricci, Alfredo

Ulivi, P.

English

Degl'Innocenti, Alessandro

Florence Research

This article was downloaded by: [Computing & Library Services, University ofHuddersfield]On: 14 January 2015, At: 00:49Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UKPhosphorus, Sulfur, and Silicon andthe Related ElementsPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/gpss20Thiosilanes Based Delivery of SulfurFunctionalities in Organic SynthesisAlessandro Degl'innocenti a , Antonella Capperucci b , PaolaUlivi b , Alessandro Mordini a , Gianna Reginato a & AlfredoRicci a ca Centro C.N.R. Composti Eterociclici c/ob Dipartimento di Chimica Organica , via G. Capponi, 9,50121, Firenze, Italyc Dipartimento di Chimica Organica , v.le Risorgimento 4,40100, Bologna, ItalyPublished online: 23 Sep 2006.To cite this article: Alessandro Degl'innocenti , Antonella Capperucci , Paola Ulivi , AlessandroMordini , Gianna Reginato & Alfredo Ricci (1993) Thiosilanes Based Delivery of SulfurFunctionalities in Organic Synthesis, Phosphorus, Sulfur, and Silicon and the Related Elements,74:1-4, 385-386, DOI: 10.1080/10426509308038127To link to this article:  http://dx.doi.org/10.1080/10426509308038127PLEASE SCROLL DOWN FOR ARTICLETaylor & Francis makes every effort to ensure the accuracy of all the information(the “Content”) contained in the publications on our platform. However, Taylor& Francis, our agents, and our licensors make no representations or warrantieswhatsoever as to the accuracy, completeness, or suitability for any purpose of theContent. Any opinions and views expressed in this publication are the opinions andviews of the authors, and are not the views of or endorsed by Taylor & Francis. Theaccuracy of the Content should not be relied upon and should be independentlyverified with primary sources of information. Taylor and Francis shall not be liablefor any losses, actions, claims, proceedings, demands, costs, expenses, damages,and other liabilities whatsoever or howsoever caused arising directly or indirectly inconnection with, in relation to or arising out of the use of the Content.This article may be used for research, teaching, and private study purposes. Anysubstantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,systematic supply, or distribution in any form to anyone is expressly forbidden.Terms & Conditions of access and use can be found at http://www.tandfonline.com/page/terms-and-conditionsDownloaded by [Computing & Library Services, University of Huddersfield] at 00:49 14 January 2015 Phosphorus, Sulfur, and Silicon, 1993, Vol. 74, pp. 385-386 0 1993 Gordon and Breach Science Publishers S.A.  Reprints available directly from the publisher Printed in the United States of America Photocopying permitted by license only THIOSIL ANES BASED DELIVERY OF SULFUR FUNCTIONALITIES IN ORGANIC SYNTHESIS. ALESSANDRO DEGL~INNOCENTI~*, ANTONELLA CAPPERUCCI~, PAOLA ULIVI~,  ALESSANDRO MORDZNI', GIANNA REGINATO' and ALFRED0 RICClaVC aCentro C.N.R. Composti Eterociclici c/o bDipartimento di Chimica Organica, via G. Capponi, 9, 50121, Firenze, Italy. CDipartimento di Chimica Organica, v.le Risorgimento 4,40100 Bologna, Italy. Abstract: Thiosilanes have been proved efficient reagents in the transfer of sulfur functionalities onto organic substrates. Vinyl sulfides have recently emerged as valuable synthetic intermediates', taking part in a number of interesting chemical transformations. Nonetheless, their synthesis is not straightforward, although a number of methodologies have been proposed in the literature2. Moreover, 1.3-bisphenylthiopropenes have been shown extremely versatile intermediates, being used by Corey3 and Cohen4 for some key steps in the total synthesis of some prostaglandin and prostacyclin systems. We report in this note on a novel synthetic approach to these classes of compounds5. We have found that upon treatment of a variety of silyl en01 ethers in the presence of equimolar amounts of BF3.Et20 with different silyl sulfides, a clean reaction occurs, leading to the corresponding substituted vinyl derivatives as shown in Scheme 1. R1, R2, R,, = Alk, Cycloalk, Ar. SCHEME 1 This reaction possesses a broad generality, occurring smoothly with different substrates, ranging from linear to cyclic enol ethers, leading to a wide variety of vinyl sulfides, a major advantage being the availability of silyl enol ethers from formally every carbonyl compound possessing an a hydrogen. Moreover, the reaction is regiospecific, as shown in the reaction of 385 Downloaded by [Computing & Library Services, University of Huddersfield] at 00:49 14 January 2015 386 A. DEGL’INNOCENTI, A. CAPPERUCCI, P.ULIVI et al. 6-methyl- 1 -c ycloexenyloxytrimethylsila~~e that affords 6-methyl- 1 -phenylthio- 1 -cycloexene exclusively. A further valuable extension of this reactivity may be achieved when reacting a-enones with 2 equivalents of PhSSiMe3. In this case, a direct and convenient entry to 1,3-bis-phenylthiopropenes can be achieved6. When using propenoylsilane as the reacting enone, the corresponding silyl derivative may be obtained in a stereospecific fashion, and the C-Si bond further functionalized to more valuable compounds or simply desilylated with retention of configuration to afford a stereospecific access to 1,3-bisphenylthiopropene formally deriving from acrolein. Alternatively treatment with t-BuLi followed by quench with SCHEME 2 different electrophiles yields functionalized silyl-bis-phenylthiopropenes which may be conveniently reacted with HgClz to afford a general entry to variously functionalized propenoylsilanes (Scheme 2). REFERENCES 1. Trost, B.M.; Lavoie, A.C. J .  Am. Chem. SOC. 1983, 105, 5075, and 2. 3. 4. 5.  6. references cited therein. Labiad, B.; Villemin, D. Synrhesis, 1989, 143, and references cited therein. Corey, E.J.; Erickson, B.W.; Noyori, R. J .  Am. Chem. SOC., 1971,93,1724. Cohen, T.; Bennet, D.A.; Mura, A.J.Jr. J .  Org. Chem., 1976, #I, 2506. Degl’Innocenti, A.; Ulivi, P.; Capperucci, A.; Mordini, A.; Reginato, G.; Ricci, A. Synlerr, 1992,499. Sato, T.; Otera, J.; Nozaki, H. Synferr, 1991,903. Downloaded by [Computing & Library Services, University of Huddersfield] at 00:49 14 January 2015 

Thiosilanes based delivery of sulfur functionalities in organic synthesis

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Thiosilanes based delivery of sulfur functionalities in organic synthesis

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