Abstract
The complex generated from BINOL, Ti(i -PrO)4 , and unactivated or a large amount of activated 4 Å MS in toluene is very effective in catalytic allylations of aldehydes using allyltributyltin. Allylations with 2.5 mol% of the catalyst provide homoallylic alcohols with greater than 95% ee. Very high syn -selective allylations of protected b-hydroxyaldehydes are achieved with 5 mol% of the BINOL/Ti(i -PrO)4 complex.
Key words
catalytic asymmetric allylation - 4 Å molecular sieves - BINOL - Ti(i -PrO)4
- allyltributyltin
References
1a Heathcock CH. In Asymmetric Synthesis
Vol. 3:
Morison JD.
Academic Press;
New York:
1984.
p.111
1b Evans DA.
Nelson JV.
Taber TR.
Top. Stereochem.
1982,
13:
1
1c Mukaiyama T.
Org. React. (N.Y.)
1982,
28:
203
2 Brown HC.
Randad RS.
Bhat KS.
Zaidlewiez M.
Racherla US.
J. Am. Chem. Soc.
1990,
112:
2389
3 Roush WR.
Hoong LK.
Palmer MAJ.
Park J.-C.
J. Org. Chem.
1990,
55:
4109
4a Riediker M.
Duthaler RO.
Angew. Chem., Int. Ed. Engl.
1989,
28:
494
4b Hafner A.
Duthaler RO.
Marti R.
Rihs J.
Rothe-Streit P.
Schwarzenbach F.
J. Am. Chem. Soc.
1992,
92:
807
4c Duthaler RO.
Hafner A.
Chem. Rev.
1992,
92:
807 ; and references cited therein
5a Furuta K.
Miwa Y.
Iwanaga K.
Yamamoto H.
J. Am. Chem. Soc.
1988,
54:
1481
5b Furuta K.
Mouri M.
Yamamoto H.
Synlett
1991,
561
5c Marshall JA.
Tang Y.
Synlett
1992,
653
5d Ishihara K.
Mouri M.
Gao Q.
Maruyama T.
Furuta K.
Yamamoto H.
J. Am. Chem. Soc.
1993,
115:
11490
5e Denmark SE.
Coe DM.
Pratt NE.
Griedel BD.
J. Org. Chem.
1994,
59:
6161
5f Kobayashi S.
Nishio K.
J. Am. Chem. Soc.
1995,
117:
6392
5g Iseki K.
Mizuno S.
Kuroki Y.
Kobayashi Y.
Tetrahedron
1999,
55:
977
5h Nakajima M.
Saito M.
Shiro M.
Hashimoto S.
J. Am. Chem. Soc.
1998,
120:
641
5i Chataigner I.
Piarulli U.
Gennari C.
Tetrahedron Lett.
1999,
120:
6419
5j Hanawa H.
Kii S.
Asao N.
Maruoka K.
Tetrahedron Lett.
2000,
41:
5543
5k Denmark SE.
Fu J.
Chem. Rev.
2003,
103:
2763 ; and references cited therein
5l Kurosu M.
Lin M.-H.
Kishi Y.
J. Am. Chem. Soc.
2004,
126:
12248 ; and references cited therein
6a Keck GE.
Tarbet KH.
Geraci LS.
J. Am. Chem. Soc.
1993,
115:
8268
6b Keck GE.
Geraci LS.
Tetrahedron Lett.
1993,
34:
7827
6c Yu C.-M.
Choi H.-S.
Yoon S.-K.
Jung W.-H.
Synlett
1997,
889
7 Costa AL.
Piazza MG.
Tagliavini E.
Trombini C.
Umani-Ronchi A.
J. Am. Chem. Soc.
1993,
115:
7001
8a Bedeschi P.
Casolari S.
Costa AL.
Tagliavini E.
Umani-Ronchi A.
Tetrahedron Lett.
1995,
36:
7897
8b Casolari S.
Cozzi GC.
Orioli P.
Tagliavini E.
Umani-Ronchi A.
Chem. Commun.
1997,
2123
8c Kurosu M.
Lorca M.
Tetrahedron Lett.
2002,
43:
1765
9 Weigand S.
Brückner R.
Chem.-Eur. J.
1996,
2:
1077
10 Terada M.
Matsumoto Y.
Nakamura Y.
Mikami K.
Inorg. Chim. Acta
1999,
296:
267
11 Powdered 4 Å MS (available from Aldrich) were used for this study.
12 In our hands the same reaction under the reported conditions by Keck
[6b R )-1-phenylhex-5-en-3-ol in 50% yield with 75.0% ee. For an analogous observation see reference 9.
13 Senko MW.
Hendrickson CL.
Emmett MR.
Shi SDH.
Marshall A.
J. Am. Soc. Mass Spectrom.
1997,
8:
970
14
1 H NMR spectra (300 MHz, CD2 Cl2 ) of (S )-BINOL and the active BINOL/Ti complex.
15a Jones AC.
Leedham TJ.
Wright PJ.
Crosbie MJ.
Fleeting KA.
Otway DJ.
O’Brien P.
Pemble ME.
J. Mater. Chem.
1998,
8:
1773
15b Hubert-Pfalzgraf LG.
J. Mater. Chem.
2004,
14:
3113 ; and references cited therein
16 Powdered 4 Å MS (available from Aldrich) were activated at 200 °C under high vacuum for 12 h, it is believed that water still remained inside activated 4 Å MS. Activated 3 Å and 5 Å MS were less effective in the formation of an active catalyst than 4 Å MS.
17 The allylstannation of hydrocinnamaldehyde using the complex generated in the presence of 50-100 mg of activated 4 Å MS [against 200 mg of (S )-BINOL] afforded (R )-1-phenylhex-5-en-3-ol in 70-80% yields with 60-70% ee. The same scale experiment using the complex generated with 150 mg of activated 4 Å MS afforded the product in 82% yield with 85% ee.
18a Molinski TF.
Searle PA.
J. Am. Chem. Soc.
1996,
118:
9422
18b Roush WR.
Champoux J.
Peterson BC.
Tetrahedron Lett.
1996,
37:
8989
19 Kurosu M.
Kishi Y.
J. Org. Chem.
1998,
63:
6100
20a Kobayashi Y.
Tan C.-H.
Kishi Y.
Angew. Chem. Int. Ed.
2000,
39:
4279
20b Higashibayashi S.
Kishi Y.
J. Am. Chem. Soc.
2003,
125:
1437 ; and references cited therein
21a Nagaoka H.
Kishi Y.
Tetrahedron
1981,
37:
3873
21b Keck GE.
Abbott DE.
Tetrahedron Lett.
1984,
25:
1883
22 (S )-BINOL was purchased from Kankyo Kagaku Center Co. Ltd.
23 Edelson BJ.
Stoltz BM.
Corey EJ.
Tetrahedron Lett.
1999,
40:
6729
