Tim den Hartog et al.
FULL PAPERS
[28] a) S. H. Hong, M. W. Day, R. H. Grubbs, J. Am. Chem.
Soc. 2004, 126, 7414–7415; b) R. Raju, L. J. Allen, T.
Le, C. D. Taylor, A. R. Howell, Org. Lett. 2007, 9,
1699–1701.
Kabeya, K. Hatano, Y. Kurono, T. Shioiri, Tetrahedron
1996, 52, 8297–8306.
[35] M. H. Junttila. O. O. E. Hormi, J. Org. Chem. 2009, 74,
3038–3047.
[29] This type of building block has been obtained (1) by
asymmetric hydrogenation in a) up to 90% ee: D. J.
Ager, S. Babler, D. E. Froen, S. A. Laneman, D. P. Pan-
taleone, I. Prakash, B. Zhi, Org. Process Res. Dev.
2003, 7, 369–378; b) up to 96% ee: X. Cheng, Q.
Zhang, J.-H. Xie, L.-X. Wang, Q.-L. Zhou, Angew.
Chem. 2005, 117, 1142–1145; Angew. Chem. Int. Ed.
2005, 44, 1118–1121; c) up to 98% ee: X. Cheng, J.-H.
Xie, S. Li, Q.-L. Zhou, Adv. Synth. Catal. 2006, 348,
1271–1276; d) up to 97% ee: ref.[9e]; e) up to 93% ee:
V. Moberg, M. Haukka, I. O. Koshevoy, R. Ortiz, E.
Nordlander, Organometallics 2007, 26, 4090–4093;
f) up to 99% ee: S. Li, S.-F. Zhu, C.-M. Zhang, S. Song,
Q.-L. Zhou, J. Am. Chem. Soc. 2008, 130, 8584–8585;
(2) enzymatically: g) K. Miyamoto, H. Ohta, J. Am.
Chem. Soc. 1990, 112, 4077–4078; h) B. Westermann,
B. Krebs, Org. Lett. 2001, 3, 189–191; i) R. Morrone,
M. Piattelli, G. Nicolosi, Eur. J. Org. Chem. 2001,
1441–1443; j) P. Beier, D. OꢂHagan, Chem. Commun.
2002, 1680–1681; k) L. M. Hutchins, L. Hunter, N.
Ehya, M. D. Gibbs, P. L. Bergquist, C. A. Hutton, Tetra-
hedron: Asymmetry 2004, 15, 2975–2980; l) E. Heden-
strçm, H. Edlund, A.-B. Wassgren, G. Bergstrçm, O.
Anderbrant, F. ꢈstrand, A. Sierpinski, M.-A. Auger-
Rozenberg, A. Herz, W. Heitland, M. Varama, J.
Chem. Ecol. 2006, 32, 2525–2541; m) S. Sabbani, E.
Hedenstrçm, O. Nordin, J. Mol. Catal. B: Enzym. 2006,
42, 1–9; (3) via DKR: n) J. Norinder, K. Bogꢀr, L.
Kanupp, J.-E. Bꢄckvall, Org. Lett. 2007, 9, 5095–5098;
(4) using a chiral auxiliary; for example: o) A. G.
Myers, B. H. Yang, H. Chen, L. McKinstry, D. J. Ko-
pecky, J. L. Gleason, J. Am. Chem. Soc. 1997, 119,
6496–6511.
[36] The observed enantioselectivities in this reaction are
representative for terminal olefins.
[37] a) J. Schuppan, H. Wehlan, S. Keiper, U. Koert, Angew.
Chem. 2001, 113, 2125–2128; Angew. Chem. Int. Ed.
2001, 40, 2063–2066; b) J. Schuppan, H. Wehlan, S.
Keiper, U. Koert, Chem. Eur. J. 2006, 12, 7364–7377.
[38] J. Barluenga, M. Alvarez-Pꢊrez, F. Rodrꢋguez, F. J.
FaÇanꢀs, J. A. Cuesta, S. Garcꢋa-Granda, J. Org. Chem.
2003, 68, 6583–6586.
[39] According to the literature, the 5-membered lactone
products possess the all-trans configuration: J.-M. Gar-
nier, S. Robin, R. Guillot, G. Rousseau, Tetrahedron:
Asymmetry 2007, 18, 1434–1442. In NOESY-NMR ex-
periments for 19 [(3R,4S)-4-iodo-3-methyldihydrofur-
an-2(3H)-one] we found a stronger coupling between
one of C5 protons and the C4 proton and a weaker
coupling with the other C5 proton and the C4 proton.
The weaker coupling is as strong as the coupling of the
protons of C4 and C3. For 22 [(3R,4S,5R)-5-hexyl-4-
iodo-3-methyldihydrofuran-2(3H)-one] we found
a
weak coupling between the protons of C5 and C4 and a
coupling similar in strength for the C4 and C3 protons.
In combination with the expected trans-conformation
for the protons of C4 and C5 arising from anti-addition
of the carboxylate on the iodonium intermediate this
most likely indicates an all-trans conformation of both
19 and 22.
[40] The bromo substituted 4-membered lactone can also be
synthesized: a) I. Shibata, M. Toyota, A. Baba, H. Mat-
suda, Chem. Express 1989, 4, 241–244; b) S. R. Melle-
gaard, J. A. Tunge, J. Org. Chem. 2004, 69, 8979–8981.
[41] D. Fischer, H. Tomeba, N. K. Pahadi, N. T. Patil, Z.
Huo, Y. Yamamoto, J. Am. Chem. Soc. 2008, 130,
15720–15725.
[42] At higher concentration using the same reagents, the 5-
membered lactone was obtained in low yield. This
product is presumably formed by iodination of the
olefin followed by SN2 attack of the carboxylate on the
terminal iodoalkane.
[30] R. W. Ficken, M. S. Ficken, J. P. Hailman, Science 1974,
183, 760–763.
[31] J. Guiard, A. Collmann, M. Gilleron, L. Mori, G. De
Libero, J. Prandi, G. Puzo, Angew. Chem. 2008, 120,
9880–9884; Angew. Chem. Int. Ed. 2008, 47, 9734–
9738.
[32] M. Arai, T. Kawasuji, E. Nakamura, J. Org. Chem.
[43] E. J. Corey, T. Hase, Tetrahedron Lett. 1979, 335–338.
[44] a) P. A. Grieco, Y. S. Hon, A. Perez-Medrano, J. Am.
Chem. Soc. 1988, 110, 1630–1631; b) K. S. Chu, G. R.
Negrete, J. P. Konopelski, J. Org. Chem. 1991, 56,
5196–5202.
[45] Using 21 (1 equiv.), I2 (5 equiv.), K3PO4 (5 equiv.),
CH2Cl2 (9.5 mM in 21), room temperature, 16 h, the 5-
membered product 22 was obtained in 77% yield.
However, this yield was calculated from an impure
spectrum containing an inseparable C11-phthalate from
the CH2Cl2 used for the work-up of this reaction.
[46] This procedure was based on a procedure described in:
S. Liu, R. P. Hanzlik J. Med. Chem. 1992, 35, 1067–
1075.
1993, 58, 5121–5129.
[33] This kind of building block has been obtained (1) using
chiral auxiliaries: a) W. Oppolzer, A. J. Kingma, G.
Poli, Tetrahedron 1989, 45, 479–488; b) S. Itꢉ, T. Tsu-
noda, Pure Appl. Chem. 1990, 62, 1405–1408; c) E. J.
Corey, D.-H. Lee, J. Am. Chem. Soc. 1991, 113, 4026–
4028; d) T. Tsunoda, M. Sakai, O. Sasaki, Y. Sako, Y.
Hondo, S. It, Tetrahedron Lett. 1992, 33, 1651–1654;
(2) via enantioselective Claisen rearrangement in up to
95% ee: e) P. Metz, B. Hungerhoff, J. Org. Chem. 1997,
62, 4442–4448.
[34] This kind of cyclic building block has been obtained (1)
enzymatically: a) H. Akita, H. Matsukura, T. Oishi,
Chem. Pharm. Bull. 1986, 34, 2656–2659; b) D. Buis-
son, S. Henrot, M. LarchevÞque, R. Azerad, Tetrahe-
dron Lett. 1987, 28, 5033–5036; (2) from the chiral
pool; c) M. LarchevÞque, S. Henrot, Tetrahedron 1987,
43, 2303–2310; d) Y. Hamada, F. Yokokawa, M.
[47] G. Sun, P. S. Savle, R. D. Gandour, N. N. a’Bhaꢋrd,
R. R. Ramsay, F. R. Fronczek, J. Org. Chem. 1995, 60,
6688–6695.
[48] A. W. van Zijl, A. J. Minnaard, B. L. Feringa, J. Org.
Chem. 2008, 73, 5651–5653.
1012
ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 999 – 1013