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
References
1a </A>
Schwartz RE.
Liesch J.
Hensens O.
Zitano L.
Honeycutt S.
Garrity G.
Fromtling RA.
Onishi J.
Monaghan R.
J. Antibiot.
1988,
41:
1774
1b </A>
Johnson JH.
Phillipson DW.
Kahle AD.
J. Antibiot.
1989,
42:
1184
<A NAME="RG09604ST-2">2 </A>
Kasahara K.
Yoshida M.
Eishima J.
Takesako K.
Beppu T.
Horinouchi S.
J. Antibiot.
1997,
50:
267
<A NAME="RG09604ST-3">3 </A>
Achenbach TV.
Slater EP.
Brummerhop H.
Bach T.
Müller R.
Antimicrob. Agents Chemother.
2000,
44:
2794
4a </A>
Pak CS.
Lee GH.
J. Org. Chem.
1991,
56:
1128
4b </A>
McGrane PL.
Livinghouse T.
J. Am. Chem. Soc.
1993,
115:
11485
4c </A>
Shimazaki M.
Okazaki F.
Nakajima F.
Ishikaya T.
Ohta A.
Heterocycles
1993,
36:
1823
4d </A>
Deng W.
Overman LE.
J. Am. Chem. Soc.
1994,
116:
11241
4e </A>
Overhand M.
Hecht SM.
J. Org. Chem.
1994,
59:
4721
4f </A>
Yoda H.
Yamazaki H.
Takabe K.
Tetrahedron: Asymmetry
1996,
7:
373
4g </A>
Beier C.
Schaumann E.
Synthesis
1997,
11:
1296
4h </A>
Kadota I.
Saya S.
Yamamoto Y.
Heterocycles
1997,
46:
335
4i </A>
Dong HQ.
Lin GQ.
Chin. J. Chem.
1998,
16:
458
4j </A>
Kanazawa A.
Gillet S.
Delair P.
Greene AE.
J. Org. Chem.
1998,
63:
4660
4k </A>
Veeresa G.
Datta A.
Tetrahedron
1998,
54:
15673
4l </A>
Verma R.
Ghosh SK.
J. Chem. Soc., Perkin Trans. 1
1999,
265
4m </A>
Lee K.-Y.
Kim Y.-H.
Oh C.-Y.
Ham W.-H.
Org. Lett.
2000,
2:
4041
4n </A>
Bach T.
Brummerhop H.
Harms K.
Chem.-Eur. J.
2000,
6:
3838
4o </A>
Okue M.
Watanabe H.
Kitahara T.
Tetrahedron
2001,
57:
4107
4p </A>
Krasinski A.
Gruza H.
Jurczak J.
Heterocycles
2001,
54:
581
4q </A>
Cadwell JJ.
Craig D.
East SP.
Synlett
2001,
1602
4r </A>
Dikshit DK.
Goswami LN.
Singh VS.
Synlett
2003,
1737
4s </A>
Raghavan S.
Rasheed MA.
Tetrahedron
2003,
59:
10307
4t </A>
Huang P.-Q.
Wu T.-J.
Ruan Y.-P.
Org. Lett.
2003,
5:
4341
5a </A>
Hafner A.
Duthaler RO.
Marti R.
Rihs G.
Rothe-Streit P.
Schwarzenbach F.
J. Am. Chem. Soc.
1992,
114:
2321
5b </A>
Duthaler RO.
Hafner A.
Chem. Rev.
1992,
92:
807
6 </A>
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.
<A NAME="RG09604ST-7">7 </A>
The enantiomeric excess of (+)-3 was determined by 1 H NMR after its derivatization with (S )- and (R )-methoxy-phenylacetic acid.
<A NAME="RG09604ST-8">8 </A>
Secondary alcohol 4′ was isolated as a mixture of two diastereomers in a 75:25 ratio. After debenzylation
(H2 , 1 H NMR and 13 C NMR data, the major product has the anti -anti structure (Figure
[3
Figure 3
9 </A>
Decomposition of the starting material or non-reactivity were observed when other
boranes were used [9-BBN, (Cy)2 BH].
<A NAME="RG09604ST-10">10 </A>
Scholl M.
Ding S.
Woo Lee S.
Grubbs RH.
Org. Lett.
1999,
1:
953
<A NAME="RG09604ST-11">11 </A>
The formation of tetrahydrofuran B as secondary product could be observed during the cyclization process (Figure
[4
Figure 4
