Communication
ChemComm
(J.M.C.) and The Tulsa Undergraduate Research Challenge
(P.A.C.). Jennifer Holland is acknowledged for assisting with
mass spectrometry.
Notes and references
1 (a) A. Fu¨rstner, Angew. Chem., Int. Ed., 2000, 39, 3012–3043; (b) R. H.
Grubbs, Tetrahedron, 2004, 60, 7117–7140; (c) K. C. Nicolaou, P. G.
Bulger and D. Sarlah, Angew. Chem., Int. Ed., 2005, 44, 4490–4527;
(d) A. H. Hoveyda and A. R. Zhugralin, Nature, 2007, 450, 243–251;
(e) A. Fu¨rstner, Chem. Commun., 2011, 47, 6505–6511.
2 C. W. Bielawski and R. H. Grubbs, Prog. Polym. Sci., 2007, 32, 1–29.
3 (a) J. B. Binder and R. T. Raines, Curr. Opin. Chem. Biol., 2008, 12,
767–773; (b) Y. A. Lin, J. M. Chalker and B. G. Davis, ChemBioChem,
2009, 10, 959–969.
4 (a) Y. A. Lin, J. M. Chalker, N. Floyd, G. J. L. Bernardes and B. G.
Davis, J. Am. Chem. Soc., 2008, 130, 9642–9643; (b) J. M. Chalker, Y. A. Lin,
O. Boutureira and B. G. Davis, Chem. Commun., 2009, 3714–3716.
5 (a) Y. A. Lin, J. M. Chalker and B. G. Davis, J. Am. Chem. Soc., 2010,
132, 16805–16811; (b) Y. A. Lin and B. G. Davis, Beilstein J. Org.
Chem., 2010, 6, 1219–1228.
6 S. B. Garber, J. S. Kingsbury, B. L. Gray and A. H. Hoveyda, J. Am.
Chem. Soc., 2000, 122, 8168–8179.
7 (a) E. Tzur, A. Szadkowska, A. Ben-Asuly, A. Makal, I. Goldberg,
K. Wo´zniak, K. Grela and N. G. Lemcoff, Chem. – Eur. J., 2010, 16,
8726–8737; (b) A. Fu¨rstner, G. Seidel and N. Kindler, Tetrahedron,
1999, 55, 8215–8230.
Scheme 2 An allyl sulphide as a traceless promoter in ring-closing metathesis.
Isolated yields are reported in (A). In (B) and (C), reaction conversions were
determined directly by 1H NMR.
8 Y. A. Lin, O. Boutureira, L. Lercher, B. Bhushan, R. S. Paton and
B. G. Davis, J. Am. Chem. Soc., 2013, 135, 12156–12159.
9 S. A. Cochrane, Z. Huang and J. C. Vederas, Org. Biomol. Chem.,
2013, 11, 630–639.
10 (a) J. Alam, T. H. Keller and T.-P. Loh, J. Am. Chem. Soc., 2010, 132,
9546–9548; (b) S. L. Mangold, D. J. O’Leary and R. H. Grubbs, J. Am.
Chem. Soc., 2014, 136, 12469–12478.
with a mere 30 minutes of reaction time. In comparison, when
diene 26 was subjected to the same reaction conditions, an
average of 63% conversion was observed over four trials. These
experiments demonstrate that not only are allyl sulphides com-
patible with relay olefin metathesis, but that the allyl sulphide
11 L. Hunter, G. C. Condie and M. M. Harding, Tetrahedron Lett., 2010,
51, 5064–5067.
promotes a rapid reaction to a ring-closed product that does not 12 (a) S. Zheng, N. Gao, W. Liu, D. Liu, X. Zhao and T. Cohen, Org. Lett.,
2010, 12, 4454–4457; (b) G. Mingat, J. J. W. McDouall and J. Clayden,
Chem. Commun., 2014, 50, 6754–6757.
13 (a) S. K. Armstrong and B. A. Christie, Tetrahedron Lett., 1996, 37,
necessarily contain sulphur. In this way, the allyl sulphide is a
traceless promoter of ring-closing olefin metathesis.
We are currently taking advantage of this strategy to enable
challenging olefin metathesis reactions on biomolecules such
as peptides and proteins that often employ or require aqueous
9373–9376; (b) Y.-S. Shon and T. R. Lee, Tetrahedron Lett., 1997, 38,
1283–1286; (c) G. Spagnol, M.-P. Heck, S. P. Nolan and C. Mioskowski,
Org. Lett., 2002, 4, 1767–1770; (d) F. D. Toste, A. K. Chatterjee and
R. H. Grubbs, Pure Appl. Chem., 2002, 74, 7–10.
media. In such cases, rapid olefin metathesis is necessary to 14 (a) T. R. Hoye, C. S. Jeffrey, M. A. Tennakoon, J. Wang and H. Zhao,
outcompete catalyst decomposition.4,5,8 In these efforts, we aim
to enable carbon–carbon formation on biomedically relevant
J. Am. Chem. Soc., 2004, 126, 10210–10211; (b) T. R. Hoye and J. Jeon,
in Metathesis in Natural Product Synthesis: Strategies, Substrates and
Catalysts, ed. J. Cossy, S. Arseniyadis and C. Meyer, Wiley, Weinheim,
molecules without requiring sulphur in the final product—a
distinction from the previously published efforts in olefin meta-
thesis on peptides and proteins highlighted in Fig. 1.4,5,8–10 Such a
strategy would expand the bioconjugate targets accessible by
olefin metathesis. More generally, we encourage consideration
of allyl sulphides as traceless promoters for olefin metathesis in
synthetic sequences where challenging or sluggish metathesis
reactions are encountered. The ease of assembly of the allyl
sulphide promoters (Schemes 1A and 2A) and the favourable
Germany, 2010, pp. 261–285.
15 For a full reference list and CAS numbers for the catalysts studied in
this report, please consult the ESI†.
16 I. C. Stewart, T. Ung, A. A. Pletnev, J. M. Berlin, R. H. Grubbs and
Y. Schrodi, Org. Lett., 2007, 9, 1589–1592.
17 J. A. Love, J. P. Morgan, T. M. Trnka and R. H. Grubbs, Angew. Chem.,
Int. Ed., 2002, 41, 4035–4037.
18 A recent report has also shown allyl sulphides as reactive substrates
with recently developed Z-selective olefin metathesis catalysts (ref. 10b).
Consistent with Table 1, this catalyst contains an NHC ligand and a
labile nitrate ligand that does not compete with the sulfide for binding
to ruthenium.
rates compared to non-relayed metathesis (24 vs. 26) bode well 19 T. Ung, A. Hejl, R. H. Grubbs and Y. Schrodi, Organometallics, 2004,
23, 5399–5401.
for productive use of this strategy in chemical synthesis.
20 (a) A. K. Chatterjee, T.-L. Choi, D. P. Sanders and R. H. Grubbs,
The authors acknowledge financial support from The
J. Am. Chem. Soc., 2003, 125, 11360–11370; (b) S. J. Connon and
University of Tulsa Faculty Development Summer Fellowship
S. Blechert, Angew. Chem., Int. Ed., 2003, 42, 1900–1923.
518 | Chem. Commun., 2015, 51, 515--518
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