Abstract
Cycloalkenones were found to react with α-lithiated diethyl (phenylselanyl)methylphosphonate
preferentially or exclusively at the carbonyl group giving 1,2-adducts. When complexes
of cycloalkenones with aluminum tris(2,6-diphenylphenoxide) were used for this reaction,
regioselective 1,4-addition was observed. Upon oxidation the thus-formed 1,4-adducts
gave the corresponding 3-(phosphorylmethyl)cycloalk-2-enones. An alternative approach
to the latter compounds involved 1,4-addition of diethyl lithiomethylphosphonate to
2-sulfinylcycloalk-2-enones followed by sulfoxide elimination.
Key words
conjugate addition - cycloalkenones - α-phosphonate carbanions - 3-phosphorylcycloalk-2-enones
References
<A NAME="RT16106SS-1">1 </A>
Mikolajczyk M.
Rev. Heteroat. Chem.
1993,
2:
19
<A NAME="RT16106SS-2">2 </A>
Mikolajczyk M.
Mikina M.
Zurawinski R.
Pure Appl. Chem.
1999,
71:
473
<A NAME="RT16106SS-3">3 </A>
Mikolajczyk M.
Mikina M.
Jankowiak A.
Mphahlele MJ.
Synthesis
2000,
1075
<A NAME="RT16106SS-4">4 </A>
Mikolajczyk M.
Mikina M.
Jankowiak A.
J. Org. Chem.
2000,
65:
5127
<A NAME="RT16106SS-5">5 </A>
Mikolajczyk M.
Mikina M.
Wieczorek MW.
Blaszczyk J.
Angew. Chem., Int. Ed. Engl.
1996,
35:
1560
<A NAME="RT16106SS-6">6 </A>
Mikolajczyk M,
Mikina M, and
Jankowiak A. inventors; PL 366,531.
<A NAME="RT16106SS-7">7 </A>
Mikolajczyk M.
Mikina M.
J. Org. Chem.
1994,
59:
6760
<A NAME="RT16106SS-8">8 </A>
Ohler E.
Zbiral E.
Synthesis
1991,
3597
<A NAME="RT16106SS-9">9 </A>
Mphahlele MJ.
Modro TA.
J. Org. Chem.
1995,
60:
8236
<A NAME="RT16106SS-10">10 </A> For a recent representative paper on this topic, see:
Modro AM.
Modro TA.
Mphahlele MJ.
Perlikowska W.
Pienaar A.
Sales M.
van Rooyen PH.
Can. J. Chem.
1998,
76:
1344 ; and references therein
<A NAME="RT16106SS-11">11 </A>
Balczewski P.
Pietrzykowski WM.
Mikolajczyk M.
Tetrahedron
1995,
51:
7727
<A NAME="RT16106SS-12">12 </A> For a review, see:
Saito S.
Yamamoto H.
Chem. Commun.
1997,
1585
<A NAME="RT16106SS-13">13 </A> For synthetic applications of selenoxide elimination, see:
Paulmier C.
Selenium Reagents and Intermediates in Organic Synthesis
Pergamon;
Oxford:
1986.
p.132-143
14a </A>
Posner GH.
Mallamo JP.
Hulce M.
Frye LL.
J. Am. Chem. Soc.
1982,
104:
4180
14b </A>
Posner GH.
Kogan TP.
Hulce M.
Tetrahedron Lett.
1984,
25:
383
14c </A>
Posner GH.
Kogan TP.
Haines SR.
Frye LL.
Tetrahedron Lett.
1984,
25:
2627
14d </A>
Posner GH.
Frye LL.
Hulce M.
Tetrahedron
1984,
40:
1041
14e </A>
Posner GH.
Asirvatham E.
J. Org. Chem.
1985,
50:
2589
14f </A>
Posner GH.
Switzer C.
J. Am. Chem. Soc.
1986,
108:
1239
14g </A>
Posner GH.
Weitzberg M.
Haill TG.
Asirvatham E.
Cun-Heng H.
Clardy J.
Tetrahedron
1986,
42:
2919
14h </A>
Posner GH.
Acc. Chem. Res.
1987,
20:
72
<A NAME="RT16106SS-15">15 </A>
Durst T. In
Comprehensive Organic Chemistry
Vol. 3:
Barton DRH.
Ollis WD.
Pergamon;
Oxford:
1979.
p.140-144
<A NAME="RT16106SS-16">16 </A>
Yechezkel T.
Ghera E.
Ostercamp D.
Hassner A.
J. Org. Chem.
1995,
60:
5135
<A NAME="RT16106SS-17">17 </A>
The starting cyclohexenyl sulfoxide was prepared by oxidation of the corresponding
sulfide according to ref. 16. However, our product was crystalline and not an oil
as reported. For full spectroscopic and analytical data, see the experimental part.
