Abstract
2,3-Dihydro-2,2-dimethyl-4H -thiopyran-4-one undergoes regiospecific photocycloaddition to 2-chloroacrylonitrile
as well as regio- and stereospecific photocycloaddition to ethylidenemalononitrile.
On irradiation in the presence of either 2,3-dimethylbuta-1,3-diene or isoprene,
the same enone affords mainly [2+2]-cycloadducts and only minor amounts of (stepwise)
[2+4]-cycloadducts, whereas quantitative quenching is observed in the presence of
2,5-dimethylhexa-2,4-diene. In contrast, the corresponding pyran is almost quantitatively
quenched in the presence of any of the enenitriles or dienes mentioned.
Key words
[2+2] photocycloaddition - 1-chlorocyclobutanecarbonitriles - vinylcyclobutanes -
1,4-biradicals
References
<A NAME="RT00607SS-1">1 </A>
Margaretha P. In
Molecular and Supramolecular Photochemistry
Vol. 12:
Griesbeck AG.
Mattay J.
Marcel Dekker;
New York:
2005.
p.211-238 ; and references cited therein
<A NAME="RT00607SS-2">2 </A>
Ciamician G.
Silber P.
Ber. Dtsch. Chem. Ges.
1908,
41:
1928
<A NAME="RT00607SS-3">3 </A>
Valenta Z.
Liu HJ.
Org. Synth., Coll. Vol. VI
John Wiley & Sons;
London:
1988.
p.1024
<A NAME="RT00607SS-4">4 </A>
Lam EYY.
Valentine D.
Hammond GS.
J. Am. Chem. Soc.
1967,
89:
3482
<A NAME="RT00607SS-5">5 </A>
Cantrell TS.
J. Org. Chem.
1974,
39:
3063
<A NAME="RT00607SS-6">6 </A>
Sano T.
Toda J.
Tsuda Y.
Chem. Pharm. Bull.
1983,
31:
2960
<A NAME="RT00607SS-7">7 </A>
Demuth M.
Pandey B.
Wietfeld B.
Said H.
Viader J.
Helv. Chim. Acta
1988,
71:
1392
<A NAME="RT00607SS-8">8 </A>
Sano T.
Horiguchi Y.
Tsuda Y.
Furuhata K.
Takayanagi H.
Ogura H.
Chem. Pharm. Bull.
1987,
35:
9
<A NAME="RT00607SS-9">9 </A>
Sano T.
Enomoto H.
Kurebayashi Y.
Horiguchi Y.
Tsuda Y.
Chem. Pharm. Bull.
1993,
41:
471
<A NAME="RT00607SS-10">10 </A>
Witte B.
Margaretha P.
Org. Lett.
1999,
1:
173
<A NAME="RT00607SS-11">11 </A>
Witte B.
Meyer L.
Margaretha P.
Helv. Chim. Acta
2000,
83:
554
<A NAME="RT00607SS-12">12 </A>
Lohmeyer B.
Schmidt K.
Margaretha P.
Helv. Chim. Acta
2006,
89:
854
<A NAME="RT00607SS-13">13 </A>
Schuster DI.
Dunn DA.
Heibel GE.
Brown PM.
Rao JM.
Woning J.
Bonneau R.
J. Am. Chem. Soc.
1991,
113:
6245
<A NAME="RT00607SS-14">14 </A>
Broeker JL.
Eksterowicz JE.
Belk AJ.
Houk KN.
J. Am. Chem. Soc.
1995,
117:
1847
<A NAME="RT00607SS-15">15 </A>
Moorthy JN.
Koner AL.
Samantha S.
Singhal N.
Nau WM.
Weiss RG.
Chem. Eur. J.
2006,
12:
8744
<A NAME="RT00607SS-16">16 </A>
Plettner E.
Mohle A.
Mwangi MT.
Griscti J.
Patrick BO.
Nair R.
Batchelor RJ.
Einstein F.
Tetrahedron: Asymmetry
2005,
16:
2754
<A NAME="RT00607SS-17">17 </A>
Freeman PK.
Balls DM.
Brown DJ.
J. Org. Chem.
1968,
33:
2211
<A NAME="RT00607SS-18">18 </A>
Damiano-Gal J.
Geribaldi S.
Torri G.
Rouillard M.
Azzaro M.
Bull. Soc. Chim. Fr.
1977,
345
<A NAME="RT00607SS-19">19 </A>
Plummer BF.
Songster M.
J. Org. Chem.
1990,
55:
1368
<A NAME="RT00607SS-20">20 </A>
Wiberg KB.
Barth DE.
Pratt WE.
J. Am. Chem. Soc.
1977,
99:
4286
<A NAME="RT00607SS-21">21 </A>
Schmidt K.
Kopf J.
Margaretha P.
Helv. Chim. Acta
2005,
88:
1922
<A NAME="RT00607SS-22">22 </A>
Miller JL.
J. Phys. Chem. A
2004,
108:
2268
<A NAME="RT00607SS-23">23 </A>
Schuster DI.
Heibel GE.
Brown PB.
J. Am. Chem. Soc.
1988,
110:
8261
<A NAME="RT00607SS-24">24 </A>
Lavilla JA.
Goodman JL.
Chem. Phys. Lett.
1987,
141:
149
<A NAME="RT00607SS-25">25 </A>
Schmidt K.
Kopf J.
Margaretha P.
Helv. Chim. Acta
2006,
89:
1927
<A NAME="RT00607SS-26">26 </A>
Kosower EM.
Sorensen TS.
J. Org. Chem.
1963,
28:
687
<A NAME="RT00607SS-27">27 </A>
Prajapati D.
Sandhu JS.
J. Chem. Soc., Perkin Trans. 1
1993,
739
<A NAME="RT00607SS-28">28 </A>
CCDC-633282 contains the supplementary crystallographic data for 5 . This data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request.cif.
<A NAME="RT00607SS-29">29 </A>
CCDC-632623 contains the supplementary crystallographic data for 10 . This data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request.cif.
