Subscribe to RSS
DOI: 10.1055/s-2004-829564
Total Synthesis of (+)-Preussin: Control of the Stereogenic Centers by Enantioselective Allyltitanations
Publication History
Publication Date:
15 July 2004 (online)
Abstract
(+)-Preussin was synthesized in ten steps with an overall yield of 6.4% from phenylacetaldehyde. The three stereogenic centers were controlled by enantioselective allyltitanations of aldehydes.
Key words
preussin - allyltitanation - cross-metathesis
-
1a
Schwartz RE.Liesch J.Hensens O.Zitano L.Honeycutt S.Garrity G.Fromtling RA.Onishi J.Monaghan R. J. Antibiot. 1988, 41: 1774 -
1b
Johnson JH.Phillipson DW.Kahle AD. J. Antibiot. 1989, 42: 1184 - 2
Kasahara K.Yoshida M.Eishima J.Takesako K.Beppu T.Horinouchi S. J. Antibiot. 1997, 50: 267 - 3
Achenbach TV.Slater EP.Brummerhop H.Bach T.Müller R. Antimicrob. Agents Chemother. 2000, 44: 2794 -
4a
Pak CS.Lee GH. J. Org. Chem. 1991, 56: 1128 -
4b
McGrane PL.Livinghouse T. J. Am. Chem. Soc. 1993, 115: 11485 -
4c
Shimazaki M.Okazaki F.Nakajima F.Ishikaya T.Ohta A. Heterocycles 1993, 36: 1823 -
4d
Deng W.Overman LE. J. Am. Chem. Soc. 1994, 116: 11241 -
4e
Overhand M.Hecht SM. J. Org. Chem. 1994, 59: 4721 -
4f
Yoda H.Yamazaki H.Takabe K. Tetrahedron: Asymmetry 1996, 7: 373 -
4g
Beier C.Schaumann E. Synthesis 1997, 11: 1296 -
4h
Kadota I.Saya S.Yamamoto Y. Heterocycles 1997, 46: 335 -
4i
Dong HQ.Lin GQ. Chin. J. Chem. 1998, 16: 458 -
4j
Kanazawa A.Gillet S.Delair P.Greene AE. J. Org. Chem. 1998, 63: 4660 -
4k
Veeresa G.Datta A. Tetrahedron 1998, 54: 15673 -
4l
Verma R.Ghosh SK. J. Chem. Soc., Perkin Trans. 1 1999, 265 -
4m
Lee K.-Y.Kim Y.-H.Oh C.-Y.Ham W.-H. Org. Lett. 2000, 2: 4041 -
4n
Bach T.Brummerhop H.Harms K. Chem.-Eur. J. 2000, 6: 3838 -
4o
Okue M.Watanabe H.Kitahara T. Tetrahedron 2001, 57: 4107 -
4p
Krasinski A.Gruza H.Jurczak J. Heterocycles 2001, 54: 581 -
4q
Cadwell JJ.Craig D.East SP. Synlett 2001, 1602 -
4r
Dikshit DK.Goswami LN.Singh VS. Synlett 2003, 1737 -
4s
Raghavan S.Rasheed MA. Tetrahedron 2003, 59: 10307 -
4t
Huang P.-Q.Wu T.-J.Ruan Y.-P. Org. Lett. 2003, 5: 4341 -
5a
Hafner A.Duthaler RO.Marti R.Rihs G.Rothe-Streit P.Schwarzenbach F. J. Am. Chem. Soc. 1992, 114: 2321 -
5b
Duthaler RO.Hafner A. Chem. Rev. 1992, 92: 807 - 10
Scholl M.Ding S.Woo Lee S.Grubbs RH. Org. Lett. 1999, 1: 953
References
Complex (R,R)-Ia (R = MOM) was formed in situ after deprotonation of 3-methoxymethoxypropene by s-BuLi and transmetallation with the correponding chlorocyclo-pentadienyldialkoxytitanium(IV) complex.
7The enantiomeric excess of (+)-3 was determined by 1H NMR after its derivatization with (S)- and (R)-methoxy-phenylacetic acid.
8Secondary alcohol 4′ was isolated as a mixture of two diastereomers in a 75:25 ratio. After debenzylation (H2,
Pd/C, quantitative yield), the resulting 1,3-diols were transformed to the corresponding acetonides (dimethoxypropane, PPTS, 90%). According to the 1H NMR and 13C NMR data, the major product has the anti-anti structure (Figure
[3]
):
Decomposition of the starting material or non-reactivity were observed when other boranes were used [9-BBN, (Cy)2BH].
11The formation of tetrahydrofuran B as secondary product could be observed during the cyclization process (Figure [4] ).