IronACHTUNGTRENNUNG(III)-Catalyzed Halogenations by Substitution of Sulfonate Esters
(CSIC) (PIE 200680I052), FICIC, MSC (RTICC RD06/
0020/1046), and the Canary Islands FUNCIS (PI 01/06) and
ACIISI (PI 2007/022). The authors thank Dr. David Tejedor
and Dr. Romen Carrillo for helpful discussions, and techni-
cian J. Alberto Ares Rial for his experimental assistance. N.
O. thanks the Canary Islands Government for a predoctoral
fellowship and A. F-V. thanks the Spanish MEC for an FPU
fellowship.
[7] Few examples are known where the stereochemical
outcome for substitution in an aliphatic secondary alco-
hol is retention of configuration. The iconic case is the
chlorosulfite decomposition: a) E. S. Lewis, C. E.
Boozer, J. Am. Chem. Soc. 1952, 74, 308–311; b) E. S.
Lewis, C. E. Boozer, J. Am. Chem. Soc. 1953, 75, 3182–
3186; c) P. R. Schreiner, P. v. R. Schleyer, R. K. Hill, J.
Org. Chem. 1993, 58, 2822–2829; d) P. R. Schreiner,
P. v. R. Schleyer, R. K. Hill, J. Org. Chem. 1994, 59,
1849–1854. Another example is the decomposition of
alkyl chloroformates: e) E. S. Lewis, W. C. Herndon,
D. C. Duffey, J. Am. Chem. Soc. 1961, 83, 1959–1961.
[8] D. C. Braddock, R. H. Pouwer, J. W. Burton, P. Broad-
with, J. Org. Chem. 2009, 74, 6042–6049.
[9] Few works have been reported on the catalytic version:
a) J. G. Lee, K. K. Kang, J. Org. Chem. 1988, 53, 3634–
3637; b) M. Labrouillꢇre, C. Le Roux, H. Gaspard-
Iloughmane, J. Dubac, Synlett 1994, 723–724; c) M.
Yasuda, S. Yamasaki, Y. Onishi, A. Baba, J. Am. Chem.
Soc. 2004, 126, 7186–7187; d) M. Yasuda, K. Shimizu,
S. Yamasaki, A. Baba, Org. Biomol. Chem. 2008, 6,
2790–2795.
References
[1] a) R. E. Moore, in: Marine Natural Products, (Ed.: P. J.
Scheuer), Academic Press, New York, 1978, Vol. 1,
pp 43–121; b) K. L. Erickson, in: Marine Natural Prod-
ucts, (Ed.: P. J. Scheuer), Academic Press, New York,
1983, Vol. V, pp 131–257; c) T. Yasumoto, M. Murata,
Chem. Rev. 1993, 93, 1897–1909; d) D. J. Faulkner, Nat.
Prod. Rep. 2002, 19, 1–48, and preceding issues.
[2] a) R. C. Larock, Comprehensive Organic Transforma-
tions, 2nd edn., Wiley-VCH, New York, 1999, pp 689–
702; b) P. L. Spargo, in: Comprehensive Organic Func-
tional Group Transformations, (Eds.: A. R. Katritzky,
O. Meth-Cohn, C. W. Rees), Pergamon, Oxford, 1995,
Vol. 2, pp 1–36; c) R. Bohlmann, in: Comprehensive
Organic Synthesis, (Eds.: B. M. Trost, I. Fleming), Per-
gamon, Oxford, 1991, Vol. 6, pp 203–223.
[3] a) B. AÇorbe, V. S. Martꢂn, J. M. Palazꢁn, J. M. Trujillo,
Tetrahedron Lett. 1986, 27, 4991–4994; b) C. E. Tonn,
J. M. Palazꢁn, C. Ruiz-Pꢀrez, M. L. Rodrꢂguez, V. S.
Martꢂn, Tetrahedron Lett. 1988, 29, 3149–3152; c) T.
Martꢂn, M. A. Soler, J. M. Betancort, V. S. Martꢂn, J.
Org. Chem. 1997, 62, 1570–1571; d) T. Martꢂn, V. S.
Martꢂn, Tetrahedron Lett. 2000, 41, 2503–2505; e) C.
Garcꢂa, T. Martꢂn, V. S. Martꢂn, J. Org. Chem. 2001, 66,
1420–1428; f) N. Ortega, T. Martꢂn, V. S. Martꢂn, Org.
Lett. 2006, 8, 871–873; g) N. Ortega, T. Martꢂn, V. S.
Martꢂn, Eur. J. Org. Chem. 2009, 8, 554–563; h) N.
Ortega, V. S. Martꢂn, T. Martꢂn, J. Org. Chem. 2010, 75,
6660–6672.
[4] a) A. P. Kozikowski, J. Lee, J. Org. Chem. 1990, 55,
863–870; b) M. Bratz, W. H. Bullock, L. E. Overman,
T. Takemoto, J. Am. Chem. Soc. 1995, 117, 5958–5966;
c) M. T. Crimmins, K. A. Emmitte, Org. Lett. 1999, 1,
2029–2032; d) M. T. Crimmins, K. A. Emmitte, J. Am.
Chem. Soc. 2001, 123, 1533–1534; e) J. Park, B. Kim,
H. Kim, S. Kim, D. Kim, Angew. Chem. 2007, 119,
4810–4812; Angew. Chem. Int. Ed. 2007, 46, 4726–
4728; f) H. Lee, K. W. Kim, J. Park, H. Kim, S. Kim, D.
Kim, X. Hu, W. Yang, J. Hong, Angew. Chem. 2008,
120, 4268–4271; Angew. Chem. Int. Ed. 2008, 47, 4200–
4203.
[10] P. O. Miranda, R. M. Carballo, V. S. Martꢂn, J. I.
Padrꢁn, Org. Lett. 2009, 11, 357–360.
[11] Chlorinations of 3b-hydroxy-5D-steroids with stoichio-
metric amounts of FeCl3 were nonetheless achieved
with moderate to good yields. However, when steroids
without the 5,6-olefinic group in their structure were
used, no transformation took place: F.-W. Liu, H.-M.
Liu, Y.-B. Zhang, J.-Y. Zhang, L.-H. Tian, Steroids,
2005, 70, 825–830.
[12] Excess of FeCl3 (400 mol%) has been used in the syn-
thesis of 1-halobicyclooctanes from the corresponding
bridgehead tosylates: W. Kraus, H. D. Grꢈf, Angew.
Chem. 1975, 87, 878–879; Angew. Chem. Int. Ed. Engl.
1975, 14, 824–825.
[13] Menthol tosylate has been shown to undergo solvolysis
with retention of configuration: S. Hiral-Starcevic, Z.
Majerski; D. E. Sunko, J. Am. Chem. Soc. 1974, 96,
3659–3661.
[14] Chlorination of menthol with PCl5 and various addi-
tives provided the chloride with retention of configura-
tion (i.e., menthyl chloride): J. G. Smith, G. F. Wright,
J. Org. Chem. 1952, 17, 1116–1121.
[15] However, when substrate 2 was subjected to Leporeꢉs
conditions (TiCl4, CH2Cl2, À788C, see ref.[6b]) a mixture
of menthyl and neomenthyl chlorides was obtained.
[16] Q. Sun, S. Cai, B. R. Peterson, Org. Lett. 2009, 11, 567–
570.
[17] (S)-(2-Bromopropyl)benzene (the opposite enantiomer
of the bromide) was obtained from an SN2 reaction of
(R)-1-phenyl-2-propanol with PPh3/CBr4, and the spe-
cific rotation was determinated: [a]2D5: +27.9 (CH2Cl2, c
2.0).
[18] D. J. Cram, J. Am. Chem. Soc. 1964, 86, 3767–3772.
[19] Due to the volatility of some of the products, the reac-
tion was poured into H2O and the aqueous phase was
extracted with CH2Cl2. The combined organic phases
were dried (MgSO4), filtered and concentrated at at-
mospheric pressure and the crude mixture was purified
by flash chromatography using pentane as eluent. Thus,
an inseparable mixture of 2-chlorooctane, 3-chlorooc-
[5] a) A. G. Martꢂnez, A. H. Fernꢃndez, M. R. ꢆlvarez,
A. G. Fraile, J. B. Calderꢁn, J. O. Barcina, Synthesis
1986, 1076–1078; b) U. Azzena, G. Delogu, G. Melloni,
O. Piccolo, Tetrahedron Lett. 1989, 30, 4555–4558.
[6] a) S. D. Lepore, A. K. Bhunia, P. Cohn, J. Org. Chem.
2005, 70, 8117–8121; b) S. D. Lepore, A. K. Bhunia, D.
Mondal, P. C. Cohn, C. Lefkowitz, J. Org. Chem. 2006,
71, 3285–3286; c) S. D. Lepore, D. Mondal, S. Y. Li,
A. K. Bhunia, Angew. Chem. 2008, 120, 7621–7624;
Angew. Chem. Int. Ed. 2008, 47, 7511–7514.
Adv. Synth. Catal. 2011, 353, 963 – 972
ꢄ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
971