M. Kurosu / Tetrahedron Letters 47 (2006) 3395–3399
3399
5. (a) Singh, J.; Bridgewater, L. C.; Patierno, S. R. Toxicol.
Sci. 1998, 45, 72; (b) O’Brien, T.; Xu, J.; Patierno, S. R.
Mol. Cell. Biochem. 2001, 222, 173.
6. (a) Blaser, H. U.; Pugin, M.; Studer, M. In Chiral Catalyst
Immobilization and Recycling; Wiley-VCH: Weinheim,
2000; p 1; (b) Sellner, H.; Rheiner, P. B.; Seebach, D.
Helv. Chim. Acta 2002, 85, 352.
7. (a) Chen, C.; Tgami, K.; Kishi, Y. J. Org. Chem. 1995, 60,
5386; (b) Sugimoto, K.; Aoyagi, S.; Kibayashi, C. J. Org.
Chem. 1997, 62, 2322; (c) Bandini, M.; Cozzi, P. G.;
Umani-Ronchi, A. Angew. Chem., Int. Ed. 2000, 39, 2325;
(d) Bandini, M.; Cozzi, P. G.; Melchiorre, P.; Morganti,
S.; Umani-Ronchi, A. Org. Lett. 2001, 3, 1153; (e) Inoue,
M.; Suzuki, T.; Nakada, M. J. Am. Chem. Soc. 2003, 125,
1140; (f) Kurosu, M.; Lin, M.-H.; Kishi, Y. J. Am. Chem.
Soc. 2004, 126, 12248.
high vacuum. The resins were placed in a flask and CH2Cl2
(10 mL), pyridine (1 mL), and Ac2O (1 mL) were added.
After 6 h, the resins were washed with water, THF–water
(3/1), THF, and EtOAc, and dried under high vacuum for
12 h to give the dipyridyl-TentaGel resins (1.16 g). Overall
yield was established to be 80% based on the elemental
analysis of total nitrogen of CrF2-dipyridyl-entaGel
(1.51%N). The dipyridyl-TentaGel resins (0.36 mmol/g,
1 g) and CrF2(Pyridine)4Br (1.2 equiv) were placed in a
flask and DMF (4 mL) was added. The reaction mixture
was warmed to 70 °C for 2 h; the reaction color (wine red)
in the solution faded into light purple. The resins were
washed with DMF, water, THF–water (3/1), THF, and
EtOAc, and dried under high vacuum for 12 h to
give the CrF2-dipyridyl-TentaGel resins (1.17 g). Total
Cr incorporated onto the dipyridyl-TentaGel resins
was established as ꢁ0.3 mmol/g by elemental analysis
of Br.
8. Glerup, J.; Josephsen, J.; Michelsen, K.; Pedersen, E.;
Scha¨ffer, C. E. Acta Chem. Scand. 1970, 24, 247.
9. Kurosu, M.; Kishi, Y., unpublished data.
13. Due to poor solubility of [Cr(pyridine)4F2]+Brꢀ in THF,
the reaction rate with [Cr(pyridine)4F2]+Brꢀ is slower than
that with 2.
10. A general procedure for the grafting of 5-amino-2,20-
bipyridine on PS-NH2 resin. To a gently stirred suspension
of PS-NH2 (1 mmol/g) in toluene–CH2Cl2 (1/1, 20 mL)
was added benzene-1,3-disulfonyl dichloride (1.1 equiv).
14. Experimental procedure for allylation of 2-octynal. To a
stirred suspension of 2 (0.3 mmol/g, 1.0 g), Mn (12 mmol)
in degassed-THF (12 mL) was added allyl bromide
(12 mmol), 2-octynal (6 mmol), and TMSCl (9 mmol).
The reaction mixture was stirred at rt for 12 h under N2.
The reaction mixture was filtrated through a glass-filter
funnel. The filtrate was evaporated in vacuo to provide a
mixture of TMS-protected and free alcohols. The remains
were washed with water, THF–water (3/1), THF, and
EtOAc; Cr-resins were separated from unreacted Mn
and dried under high vacuum for reusing. The obtained
products were dissolved in THF (40 mL), and 3 (1.7 mmol/
g, 4.2 g) was added. After 3 h, the reaction mixture was
filtered and evaporated in vacuo to give undec-1-en-5-yn-4-
ol in 97% yield based on 1H NMR analysis.
15. Among a variety of polymer-supported ammonium fluo-
rides synthesized from the chloromethylated polystyrene,
3 exhibited excellent reactivities in the cleavage of TMS
ethers of secondary alcohols. TBDPS group was not
cleaved with 3.
16. Total Cr contaminated in the isolated products was less
than 0.01 ppm.
17. (a) Mandai, T.; Nokami, J.; Yano, T.; Yoshinaga, Y.;
Otera, J. J. Org. Chem. 1984, 49, 172; (b) Namba, K.; Cui,
S.; Wang, J.; Kishi, Y. Org. Lett. 2005, 7, 5417, and
references cited therein.
i
After 30 min at rt, PrNEt (0.5 equiv) was added into the
reaction mixture. The reaction was stirred for 6 h and 5-
amino-2,20-bipyridine (1.1 equiv) was added. After 1 h,
iPrNEt (0.5 equiv) was added into the reaction mixture
and stirred for an additional 6 h. The resins were washed
with water, THF–water (3/1), THF, and EtOAc, and dried
under high vacuum. The resins were placed in a flask and
CH2Cl2 (10 mL), pyridine (1 mL), and Ac2O (1 mL) were
added. After 6 h, the resins were washed with water, THF–
water (3/1), THF, and EtOAc, and dried under high
vacuum for 12 h.
11. (a) Liu, H.; Montaser, A. J. Anal. Spectrom. 1996, 11, 307;
(b) Boonen, S.; Vanhaecke, F.; Moens, L.; Dams, R.
Spectrochim. Acta 1996, 51, 271.
12. CrF2-dipyridyl-TentaGel resin 2. To a gently stirred
suspension of TentaGel-NH2 (0.45 mmol/g, 1 g) in tolu-
ene–CH2Cl2 (1/1, 20 mL) was added benzene-1,3-disulfo-
nyl dichloride (1.1 equiv). After 30 min at rt, iPrNEt
(0.5 equiv) was added into the reaction mixture. The
reaction was stirred for 6 h and 5-amino-2,20-bipyridine
i
(1.1 equiv) was added. After 1 h, PrNEt (0.5 equiv) was
added into the reaction mixture and stirred for an
additional 6 h. The resins were washed with water,
THF–water (3/1), THF, and EtOAc, and dried under
Kurosu, Michio
