Organic Letters
Letter
donors. For a review, see: Jensen, K. J. J. Chem. Soc., Perkin Trans. 1 2002,
2219.
Research Fellowship, and M.C.G. thanks the EPSRC CAF EP/
L001926/1 and EPSRC EP/J002542/1 (M.C.G., S.M.) for
funding. We thank Dr. Hazel Sparkes (University of Bristol) for
XRDS (10a).
(18) The primary C6-OH is amenable to conventional SN2 chemistry
to access C6-O-aryl ethers, typically with p-methoxyphenol under
Mitsunobu conditions. For a representative example, see: Clausen, M.
H.; Jørgensen, M. R.; Thorsen, J.; Madsen, R. J. Chem. Soc., Perkin Trans.
1 2001, 543.
REFERENCES
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(19) Selected example: Shi, H.; Zhou, B.; Li, W.; Shi, Z.; Yu, B.; Wang,
(1) Williamson, A. Justus Liebigs Ann. Chem. 1851, 77, 37.
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(2) (a) The Chemistry of the Ether Linkage; Patai, S., Ed.; John Wiley &
Sons Ltd.: New York, 1967. (b) For a review on metal-catalyzed aryl
ether synthesis, see: Hartwig, J. F. Angew. Chem., Int. Ed. 1998, 37, 2046.
(3) (a) Lovering, F.; Bikker, J.; Humblet, C. J. Med. Chem. 2009, 52,
6752. (b) Lednicer, D. Strategies for Organic Drug Synthesis and Design,
2nd ed.; John Wiley & Sons, Inc.: New York, 2008. (c) Roughley, S. D.;
Jordan, A. M. J. Med. Chem. 2011, 54, 3451. (d) Heterocyclic Chemistry in
Drug Discovery; Li, J. J., Ed.; Wiley-Blackwell: New York, 2013.
(4) Selected examples: (a) Maligres, P. E.; Li, J.; Krska, S. W.; Schreier,
J. D.; Raheem, I. T. Angew. Chem., Int. Ed. 2012, 51, 9071. (b) Wu, X.;
Fors, B. P.; Buchwald, S. L. Angew. Chem., Int. Ed. 2011, 50, 9943.
(c) Torraca, K. E.; Huang, X.; Parrish, C. A.; Buchwald, S. L. J. Am. Chem.
Soc. 2001, 123, 10770. (d) Terrett, J. A.; Cuthbertson, J. D.; Shurtleff, V.
W.; MacMillan, D. W. C. Nature 2015, 524, 330.
̌
(20) Review: Cerny, M. Advances in Carbohydrate Chemistry and
́
Biochemistry; Horton, D., Ed.; Academic Press: New York, 2003; Vol. 58,
p 121.
(21) Haines, A. H.; Symes, K. C. J. Chem. Soc., Perkin Trans. 1 1973, 53.
(22) (a) Hamashima, Y.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc.
2000, 122, 7412. (b) Hamashima, Y.; Kanai, M.; Shibasaki, M.
Tetrahedron Lett. 2001, 42, 691.
(23) The reactions were generally fast (<3 h). However, prolonged
reaction times were not detrimental to yield and were often used for
convenience.
(24) Where applicable, product ether regioselectivity was assigned by
13C NMR coupling constants. See: Pretsch, E.; Buhlmann, P.;
̈
Badertscher, M. Structure Determination of Organic Compounds, 4th
ed.; Springer: New York, 2009.
(5) Selected reviews: (a) Hartwig, J. F. Nature 2008, 455, 314.
(b) Monnier, F.; Taillefer, M. Angew. Chem., Int. Ed. 2009, 48, 6954.
(6) (a) Merritt, E. A.; Olofsson, B. Angew. Chem., Int. Ed. 2009, 48,
9052. (b) Lindstedt, E.; Ghosh, R.; Olofsson, B. Org. Lett. 2013, 15,
6070. (c) Ghosh, R.; Lindstedt, E.; Jalalian, N.; Olofsson, B.
ChemistryOpen 2014, 3, 54. (d) Sundalam, S. K.; Stuart, D. R. J. Org.
Chem. 2015, 80, 6456.
(25) Reaction of 1,2,3-trifluorobenzene with 4 yielded separable
(26) 1,4-Difluorobenzene was unreactive under the reaction
conditions.
(27) The bis-etherified product resulting from reaction of 1,2,4,5-
tetrafluorobenzene with 4 yielded nonseparable regioisomeric products.
(28) In DMF, reaction between equimolar quantities of 4 and 1,2,3,5-
tetrafluorobenzene afforded a mixture (∼2:1) of mono- and bis-
etherification products.
́
(7) Selected example: Cano, R.; Ramon, D. J.; Yus, M. J. Org. Chem.
2011, 76, 654.
(8) Selected SNAr examples: (a) Raeppel, S.; Raeppel, F.; Suffert, J.
Synlett 1998, 1998, 794. (b) Woiwode, T. F.; Rose, C.; Wandless, T. J. J.
Org. Chem. 1998, 63, 9594. (c) Rodriguez, J. R.; Agejas, J.; Bueno, A. B.
Tetrahedron Lett. 2006, 47, 5661. (d) Ouellet, S. G.; Bernardi, A.;
Angelaud, R.; O’Shea, P. D. Tetrahedron Lett. 2009, 50, 3776.
(9) (a) Smith, M. B.; March. J. March’s Advanced Organic Chemistry:
Reactions, Mechanisms, and Structure, 6th ed.; John Wiley & Sons, Inc.:
New York, 2007; pp 853. SNAr reviews:. (b) Vlasov, V. M. J. Fluorine
Chem. 1993, 61, 193. (c) Vlasov, V. M. Russ. Chem. Rev. 2003, 72, 681.
(10) Reviews on SNAr with metal-complexed aromatics: (a) Rose-
Munch, F.; Rose, E. Eur. J. Inorg. Chem. 2002, 2002, 1269. (b) Rosillo,
(29) A representative example rearrangement of a furanoside to the
corresponding pyranose is contained within the Supporting Information
of ref 12. See also: Cai, Y.; Ling, C.-C.; Bundle, D. R. Org. Lett. 2005, 7,
4021.
(30) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc.
Rev. 2008, 37, 320.
(31) Privileged Chiral Ligands Catalysis; Zhou, Q.-L., Ed.; Wiley-VCH:
Weinheim, 2011.
(32) Woodmansee, D. H.; Pfaltz, A. Top. Organomet. Chem. 2011, 34,
31.
(33) Koert, U. Isomannide and Isosorbide. In e-EROS Encyclopedia of
Reagents for Organic Synthesis, 2012. DOI: 10.1002/
́
M.; Domínguez, G.; Perez-Castells, J. Chem. Soc. Rev. 2007, 36, 1589.
(11) Mitsunobu approach: (a) Manivel, P.; Rai, N. P.; Jayashankara, V.
P.; Arunachalam, P. N. Tetrahedron Lett. 2007, 48, 2701. Other methods
of activation have also been used: (b) Shintou, T.; Mukaiyama, T. J. Am.
Chem. Soc. 2004, 126, 7359. (c) Sach, N. W.; Richter, D. T.; Cripps, S.;
́
Tran-Dube, M.; Zhu, H.; Huang, B.; Cui, J.; Sutton, S. C. Org. Lett. 2012,
14, 3886. (d) Shen, X.; Neumann, C. N.; Kleinlein, C.; Goldberg, N. W.;
Ritter, T. Angew. Chem., Int. Ed. 2015, 54, 5662.
(12) Henderson, A. S.; Bower, J. F.; Galan, M. C. Org. Biomol. Chem.
2014, 12, 9180.
(13) Selected examples: (a) Galan, M. C.; Tran, A. T.; Bernard, C.
Chem. Commun. 2010, 46, 8968. (b) Galan, M. C.; Benito-Alifonso, D.;
Watt, G. M. Org. Biomol. Chem. 2011, 9, 3598. (c) Galan, M. C.; Tran, A.
T.; Bromfield, K.; Rabbani, S.; Ernst, B. Org. Biomol. Chem. 2012, 10,
7091. (d) Benito-Alifonso, D.; Tremel, S.; Hou, B.; Lockyear, H.;
Mantell, J.; Fermin, D. J.; Verkade, P.; Berry, M.; Galan, M. C. Angew.
Chem., Int. Ed. 2014, 53, 810.
(14) Wuts, P. G. M.; Greene, T. W. Greene’s Protective Groups in
Organic Synthesis, 4th ed.; John Wiley & Sons, Inc.: New York, 2006.
(15) Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem., Int. Ed.
2001, 40, 2004.
(16) Anomeric glycosylation with phenols is readily achieved via
oxonium intermediates: Jacobsson, M.; Malmberg, J.; Ellervik, U.
Carbohydr. Res. 2006, 341, 1266.
(17) Several reports outline SNAr reactions of highly electron-deficient
fluoroaromatics with anomeric hydroxyls to afford reactive glycosyl
D
Org. Lett. XXXX, XXX, XXX−XXX