Synthesis of Fluoroolefins
via Julia-Kocienski Olefination

Barbara Zajc; Rakesh Kumar

doi:10.1055/s-0029-1218789

SPECIALTOPIC

Synthesis of Fluoroolefins via Julia-Kocienski Olefination

Barbara Zajc*, Rakesh Kumar
Department of Chemistry, The City College and The City University of New York, 160 Convent Avenue, New York, NY 10031, USA
Fax: +1(212)6506107; e-Mail: barbaraz@sci.ccny.cuny.edu;

Abstract

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Abstract

The Julia-Kocienski olefination provides a versatile platform for the synthesis of fluorovinyl compounds. This review describes our efforts as well as those of others in the synthesis of various fluorinated aryl and heteroaryl sulfones and their utility as olefination reagents for the modular assembly of fluoroalkenes. Where data is available, the influence of the fluorine atom on the reactivity of the olefination reagents and the stereochemical outcome of the olefination are described.

1 Introduction

2 Synthesis of Fluorostilbene-like and Fluorostyrene-like Derivatives

3 Synthesis of Fluoroalkylidenes

3.1 Benzothiazole-Based Reagents

3.2 Phenyltetrazole-Based Reagents

4 Synthesis of Functionalized Fluoroolefins

4.1 α-Fluoroacrylates

4.1.1 Benzothiazole- and Phenyltetrazole-Based Reagents

4.1.2 Bis(trifluoromethyl)phenyl-Based Reagents

4.2 α-Fluoroacrylonitriles

4.3 α-Fluorovinyl Phenyl Sulfones

4.4 α-Fluorovinyl Weinreb Amides

4.4.1 Bis(trifluoromethyl)phenyl-Based Reagent

4.4.2 Benzothiazole-Based Reagent

4.5 α-Fluoroenones

5 Synthesis of 1,1-Difluoroalkenes

6 Mechanism of Julia-Kocienski Olefination

7 Miscellaneous Syntheses of Heteroaryl-Derived Fluorinated Sulfides and Sulfones

8 Conclusions

Key words

Julia-Kocienski olefination - fluoroalkenes - fluoro sulfones - alkenation reagents - electrophilic fluorination

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Referenzen

References

<A NAME="RC00510SS-1A">1a</A> Smart BE. J. Fluorine Chem. 2001, 109: 3

<A NAME="RC00510SS-1B">1b</A> Lemal DM. J. Org. Chem. 2004, 69: 1

<A NAME="RC00510SS-2A">2a</A> Kirsch P. Modern Fluoroorganic Chemistry. Synthesis, Reactivity, Applications Wiley-VCH; Weinheim: 2004.

<A NAME="RC00510SS-2B">2b</A> Fluorine in Organic Chemistry Chambers RD. Blackwell; Oxford: 2004.

<A NAME="RC00510SS-2C">2c</A> Advances in Organic Synthesis: Modern Organofluorine Chemistry - Synthetic Aspects Vol. 2: Laali KK. Bentham Science Publishers; Bussum: 2006.

<A NAME="RC00510SS-2D">2d</A> Current Fluoroorganic Chemistry: New Synthetic Directions, Technologies, Materials, and Biological Applications Soloshonok VA. Mikami K. Yamazaki T. Welch JT. Honek JF. American Chemical Society; Washington DC: 2007.

See, for example, the following:

<A NAME="RC00510SS-3A">3a</A> Jeschke P. ChemBioChem 2004, 5: 570

<A NAME="RC00510SS-3B">3b</A> Bégué J.-P. Bonnet-Delpon D. J. Fluorine Chem. 2006, 127: 992

<A NAME="RC00510SS-3C">3c</A> Bégué J.-P. Bonnet-Delpon D. Bioorganic and Medicinal Chemistry of Fluorine John Wiley & Sons; Hoboken NJ: 2008.

Special issue on Fluorinated Synthons, J. Fluorine Chem. 2004, 125, 477.

<A NAME="RC00510SS-4B">4b</A> Fluorine-Containing Synthons Soloshonok VA. American Chemical Society; Washington DC: 2005.

See for example:

<A NAME="RC00510SS-5A">5a</A> Selective Fluorination in Organic and Bioorganic Chemistry Welch JT. American Chemical Society; Washington DC: 1991.

<A NAME="RC00510SS-5B">5b</A> Berkowitz DB. Karukurichi KR. de la Salud-Bea R. Nelson DL. McCune CD. J. Fluorine Chem. 2008, 129: 731

<A NAME="RC00510SS-6">6</A> Mikami K. Itoh Y. Yamanaka M. Chem. Rev. 2004, 104: 1

<A NAME="RC00510SS-7">7</A> Burton DJ. Yang Z.-Y. Qiu W. Chem. Rev. 1996, 96: 1641

<A NAME="RC00510SS-8A">8a</A> Blakemore PR. J. Chem. Soc., Perkin Trans. 1 2002, 2563

<A NAME="RC00510SS-8B">8b</A> Plesniak K. Zarecki A. Wicha J. Top. Curr. Chem. 2007, 275: 163

<A NAME="RC00510SS-8C">8c</A> Aïssa C. Eur. J. Org. Chem. 2009, 1831

<A NAME="RC00510SS-9">9</A> Baudin JB. Hareau G. Julia SA. Ruel O. Tetrahedron Lett. 1991, 32: 1175

<A NAME="RC00510SS-10">10</A> Blakemore PR. Cole WJ. Kocienski PJ. Morley A. Synlett 1998, 26

<A NAME="RC00510SS-11">11</A> Kocienski PJ. Bell A. Blakemore PR. Synlett 2000, 365

<A NAME="RC00510SS-12A">12a</A> Baudin JB. Hareau G. Julia SA. Ruel O. Bull. Soc. Chim. Fr. 1993, 130: 336

<A NAME="RC00510SS-12B">12b</A> Baudin JB. Hareau G. Julia SA. Lorne R. Ruel O. Bull. Soc. Chim. Fr. 1993, 130: 856

<A NAME="RC00510SS-13A">13a</A> Alonso DA. Nájera C. Varea M. Tetrahedron Lett. 2004, 45: 573

<A NAME="RC00510SS-13B">13b</A> Alonso DA. Fuensanta M. Nájera C. Varea M. J. Org. Chem. 2005, 70: 6404

<A NAME="RC00510SS-14">14</A> Makosza M. Bujok R. Synlett 2008, 586

<A NAME="RC00510SS-15">15</A> Mirk D. Grassot J.-M. Zhu J. Synlett 2006, 1255

<A NAME="RC00510SS-16">16</A> Chevrie D. Lequeux T. Demoute JP. Pazenok S. Tetrahedron Lett. 2003, 44: 8127

<A NAME="RC00510SS-17">17</A> Pazenok S, Demoute JP, Zard S, and Lequeux T. inventors; WO 0,240,459. ; Chem. Abstr. 2002, 136, 386131

<A NAME="RC00510SS-18">18</A> Ghosh AK. Zajc B. Org. Lett. 2006, 8: 1553

<A NAME="RC00510SS-19A">19a</A> Differding E. Rüegg GM. Tetrahedron Lett. 1991, 32: 3815

<A NAME="RC00510SS-19B">19b</A> Differding E. Wehrli M. Tetrahedron Lett. 1991, 32: 3819

<A NAME="RC00510SS-20">20</A> Zajc B. J. Org. Chem. 1999, 64: 1902

<A NAME="RC00510SS-21">21</A> First reported syntheses of 8-fluoro-2′-deoxynucleosides: Ghosh AK. Lagisetty P. Zajc B. J. Org. Chem. 2007, 72: 8222

<A NAME="RC00510SS-22">22</A> Anbarasan P. Neumann H. Beller M. Angew. Chem. Int. Ed. 2010, 49: 2219

<A NAME="RC00510SS-23A">23a</A> Umemoto T. Kawada K. Tomita K. Tetrahedron Lett. 1986, 27: 4465

<A NAME="RC00510SS-23B">23b</A> Umemoto T. Fukami S. Tomizawa G. Harasawa K. Kawada K. Tomita K. J. Am. Chem. Soc. 1990, 112: 8563

<A NAME="RC00510SS-23C">23c</A> Umemoto T. N-Fluoropyridinium Salts, Synthesis and Fluorination Chemistry, In Advances in Organic Synthesis: Modern Organofluorine Chemistry - Synthetic Aspects Vol. 2: Laali K. Bentham Science Publishers; Bussum: 2006. p.159-181

<A NAME="RC00510SS-24">24</A> Yamada S. Gavryushin A. Knochel P. Angew. Chem. Int. Ed. 2010, 49: 2215

<A NAME="RC00510SS-25A">25a</A> Liu P. Jacobsen EN. J. Am. Chem. Soc. 2001, 123: 10772

<A NAME="RC00510SS-25B">25b</A> Albrecht BK. Williams RM. Proc. Natl. Acad. Sci. U.S.A. 2004, 101: 11949

<A NAME="RC00510SS-26">26</A> Demoute JP, Adams A, Demassey J, and Babin D. inventors; WO 9,932,426. ; Chem. Abstr. 1999, 131, 73815

<A NAME="RC00510SS-27">27</A> Calata C. Catel J.-M. Pfund E. Lequeux T. Tetrahedron 2009, 65: 3967

<A NAME="RC00510SS-28">28</A> Ghosh AK. Zajc B. J. Org. Chem. 2009, 74: 8531

<A NAME="RC00510SS-29">29</A> Blakemore PR. Ho DKH. Nap WM. Org. Biomol. Chem. 2005, 3: 1365

<A NAME="RC00510SS-30">30</A> Zajc B. Kake S. Org. Lett. 2006, 8: 4457

<A NAME="RC00510SS-31">31</A> Ito H. Saito A. Taguchi T. Tetrahedron: Asymmetry 1998, 9: 1989

<A NAME="RC00510SS-32A">32a</A> Pfund E. Lebargy C. Rouden J. Lequeux T. J. Org. Chem. 2007, 72: 7871

In our original report (ref. 30) we stated that ketones were unreactive under the reaction conditions. Recent re-evaluation using cyclohexanone and 15 did afford the fluoroalkene in 47% isolated yield (comparable to 57% reported in ref. 27).

<A NAME="RC00510SS-33">33</A> Alonso DA. Fuensanta M. Gómez-Bengoa E. Nájera C. Adv. Synth. Catal. 2008, 350: 1823

<A NAME="RC00510SS-34">34</A> Alonso DA. Fuensanta M. Gómez-Bengoa E. Nájera C. Eur. J. Org. Chem. 2008, 2915

<A NAME="RC00510SS-35">35</A> He M. Ghosh AK. Zajc B. Synlett 2008, 999

<A NAME="RC00510SS-36A">36a</A> Patrick TB. Nadji S. J. Fluorine Chem. 1990, 49: 147

<A NAME="RC00510SS-36B">36b</A> Xu Z.-Q. DesMarteau DD. J. Chem. Soc., Perkin Trans. 1 1992, 313

<A NAME="RC00510SS-37">37</A> van Steenis JH. van den Nieuwendijk AMCH. van der Gen A. J. Fluorine Chem. 2004, 125: 107

<A NAME="RC00510SS-38">38</A> del Solar M. Ghosh AK. Zajc B. J. Org. Chem. 2008, 73: 8206

<A NAME="RC00510SS-39">39</A> Olah GA. Narang SC. Fung AP. Balaram Gupta BG. Synthesis 1980, 657

<A NAME="RC00510SS-40A">40a</A> Koizumi T. Hagi T. Horie Y. Takeuchi Y. Chem. Pharm. Bull. 1987, 35: 3959

<A NAME="RC00510SS-40B">40b</A> McCarthy JR. Matthews DP. Edwards ML. Stemerick DM. Jarvi ET. Tetrahedron Lett. 1990, 31: 5449

<A NAME="RC00510SS-40C">40c</A> Asakura N. Usuki Y. Iio H. J. Fluorine Chem. 2003, 124: 81

<A NAME="RC00510SS-40D">40d</A> Andrei D. Wnuk SF. J. Org. Chem. 2006, 71: 405

<A NAME="RC00510SS-41A">41a</A> Inbasekaran M. Peet NP. McCarthy JR. LeTourneau ME. J. Chem. Soc., Chem. Commun. 1985, 678

<A NAME="RC00510SS-41B">41b</A> Prakash GKS. Chacko S. Vaghoo H. Shao N. Gurung L. Mathew T. Olah GA. Org. Lett. 2009, 11: 1127

<A NAME="RC00510SS-42">42</A> Prakash GKS. Wang F. Shao N. Mathew T. Rasul G. Haiges R. Stewart T. Olah GA. Angew. Chem. Int. Ed. 2009, 48: 5358

<A NAME="RC00510SS-43">43</A> Manjunath BN. Sane NP. Aidhen IS. Eur. J. Org. Chem. 2006, 2851

<A NAME="RC00510SS-44">44</A> Ghosh AK. Banerjee S. Sinha S. Kang SB. Zajc B. J. Org. Chem. 2009, 74: 3689

<A NAME="RC00510SS-45">45</A> Van der Veken P. Senten K. Kertèsz I. De Meester I. Lambeir A.-M. Maes M.-B. Scharpé S. Haemers A. Augustyns K. J. Med. Chem. 2005, 48: 1768

<A NAME="RC00510SS-46">46</A> Zhao Y. Huang W. Zhu L. Hu J. Org. Lett. 2010, 12: 1444

<A NAME="RC00510SS-47">47</A> Furukawa T. Goto Y. Kawazoe J. Tokunaga E. Nakamura S. Yang Y. Du H. Kakehi A. Shiro M. Shibata N. Angew. Chem. Int. Ed. 2010, 49: 1642

<A NAME="RC00510SS-48">48</A> Castejon HJ. Wiberg KB. J. Org. Chem. 1998, 63: 3937

For the purpose of comparison, 2-naphthaldehyde was reacted with 15 in the presence of MgBr₂, using the same conditions as those reported for 47 (ref. 35). Fluoroalkene was obtained in 14:86 E/Z ratio, consistent with reported results (ref. 32a).

<A NAME="RC00510SS-50">50</A> Calata C. Pfund E. Lequeux T. J. Org. Chem. 2009, 74: 9399

<A NAME="RC00510SS-51">51</A> Petko KI. Yagupol’skii LM. Russ. J. Org. Chem. (Engl. Transl.) 2004, 40: 601 ; Zh. Org. Khim. 2004, 40, 627

<A NAME="RC00510SS-52A">52a</A> Petko KI. Yagupolskii LM. J. Fluorine Chem. 2001, 108: 211

<A NAME="RC00510SS-52B">52b</A> Dransch G, Hörlein G, Emmel L, and Bonin W. inventors; DE 2,334. ; Chem. Abstr. 1975, 83, 10056

<A NAME="RC00510SS-53">53</A> Zhang W. Wang F. Hu J. Org. Lett. 2009, 11: 2109

<A NAME="RC00510SS-54">54</A> Zhang W. Zhu L. Hu J. Tetrahedron 2007, 63: 10569

<A NAME="RC00510SS-55">55</A> Hou Y. Higashiya S. Fuchigami T. J. Org. Chem. 1997, 62: 9173

<A NAME="RC00510SS-56">56</A> Riyadh SM. Ishii H. Fuchigami T. Tetrahedron 2001, 57: 8817

<A NAME="RC00510SS-57">57</A> Zagipa B. Nagura H. Fuchigami T. J. Fluorine Chem. 2007, 128: 1168

<A NAME="RC00510SS-58">58</A> Hidaka A. Zagipa B. Nagura H. Fuchigami T. Synlett 2007, 1148

<A NAME="RC00510SS-59">59</A> Nagura H. Fuchigami T. Synlett 2008, 1714

<A NAME="RC00510SS-60">60</A> Dawood KM. Higashiya S. Hou Y. Fuchigami T.
J. Org. Chem. 1999, 64: 7935

<A NAME="RC00510SS-61">61</A> Sawamura T. Kuribayashi S. Inagi S. Fuchigami T. Org. Lett. 2010, 12: 644

<A NAME="RC00510SS-62">62</A> Wnuk SF. Bergolla LA. Garcia PI. J. Org. Chem. 2002, 67: 3065

<A NAME="RC00510SS-63">63</A> Wnuk SF. Garcia PI. Wang Z. Org. Lett. 2004, 6: 2047