References
<A NAME="RD02905ST-1">1</A>
Shapiro RH.
Org. React.
1976,
23:
405
<A NAME="RD02905ST-2A">2a</A>
Shapiro RH.
Duncan JH.
Clopton JC.
J. Am. Chem. Soc.
1967,
89:
1442
<A NAME="RD02905ST-2B">2b</A>
Shapiro RH.
Heath MJ.
J. Am. Chem. Soc.
1967,
89:
5734
<A NAME="RD02905ST-3">3</A>
Bamford WR.
Stevens TS.
J. Chem. Soc.
1952,
4735
<A NAME="RD02905ST-4">4</A>
Gianturco MA.
Friedel P.
Flanagan V.
Tetrahedron Lett.
1965,
6:
1847
<A NAME="RD02905ST-5">5</A>
Johnson PY.
Koza E.
J. Org. Chem.
1973,
38:
2967
<A NAME="RD02905ST-6">6</A>
Ogata T.
Kawata K.
Oshikawa T.
Yoshida H.
Inokawa S.
Nippon Kagaku Kaishi
1987,
7:
1370
<A NAME="RD02905ST-7">7</A>
Happman A.
Weyerstahl P.
Zummack W.
Justus Liebigs Ann. Chem.
1977,
9:
1547
<A NAME="RD02905ST-8">8</A>
von Luttringhaus A.
Prinzbach H.
Justus Liebigs Ann. Chem.
1959,
624:
79
<A NAME="RD02905ST-9A">9a</A>
Brandstrom A.
Junggern U.
Acta Chem. Scand.
1969,
23:
3585
<A NAME="RD02905ST-9B">9b</A>
Ruzicka J.
Koutek B.
Streinz L.
Saman D.
Leseticky L.
Tetrahedron: Asymmetry
1999,
10:
3521
<A NAME="RD02905ST-9C">9c</A>
Matsuama H.
Takei Y.
Kobayashi M.
Bull. Chem. Soc. Jpn.
1986,
59:
2657
<A NAME="RD02905ST-10A">10a</A>
Krapcho AP.
Synthesis
1982,
805
<A NAME="RD02905ST-10B">10b</A>
Krapcho AP.
Synthesis
1982,
893
<A NAME="RD02905ST-11">11</A>
van der Eycken E.
De Wilde H.
Deprez L.
Vandewalle M.
Tetrahedron Lett.
1987,
28:
4759
Reviews:
<A NAME="RD02905ST-12A">12a</A>
Schmidt U.
Grafen P.
Altland K.
Goedde HW.
Adv. Enzymol.
1969,
32:
423
<A NAME="RD02905ST-12B">12b</A>
Sigel H.
Angew. Chem., Int. Ed. Engl.
1982,
21:
389
<A NAME="RD02905ST-13A">13a</A>
Yadav JS.
Mysorekar SV.
Garyali K.
J. Sci. Ind. Res.
1990,
49:
400
<A NAME="RD02905ST-13B">13b</A>
Brookes MH.
Golding BT.
Howes DA.
Hudson AT.
J. Chem. Soc., Chem. Commun.
1983,
1051
<A NAME="RD02905ST-13C">13c</A>
Brookes MH.
Golding BT.
Hudson AT.
J. Chem. Soc., Perkin Trans. 1
1988,
9
<A NAME="RD02905ST-14A">14a</A>
Fadanavis NW.
Babu RL.
Vadivel SK.
Deshpande AA.
Bhalerao UT.
Tetrahedron: Asymmetry
1998,
9:
4109
<A NAME="RD02905ST-14B">14b</A>
Chavan SP.
Praveen C.
Ramakrishna G.
Kalkote UR.
Tetrahedron Lett.
2004,
45:
6027 ; and the references cited therein
<A NAME="RD02905ST-15A">15a</A>
Christian F,
Walther S, and
Hans S. inventors; Ger. Offen. DE 10150063/18.
<A NAME="RD02905ST-15B">15b</A>
Klatt M, and
Niebel M. inventors; PCT Int. Appl. WO 2003048102/17.
<A NAME="RD02905ST-16">16</A>
Kawai M.
Rev. Int. Serv. Sante Armees Terre, Mer Air
1966,
39:
861 ; Chem. Abstr. 1966, 66, 93545g
<A NAME="RD02905ST-17">17</A>
Natraj CV.
Gandhi VM.
Menon KKG.
J. Biosciences
1984,
6:
37
<A NAME="RD02905ST-18">18</A>
Wagh SS.
Natraj CV.
Menon KKG.
J. Biosciences
1987,
11:
59
<A NAME="RD02905ST-19">19</A>
Baur A.
Harrer T.
Peukert M.
Jahn G.
Kalden JR.
Fleckenstein B.
Klin. Wochenschr.
1991,
69:
722 ; Chem. Abstr. 1992, 116, 207360
<A NAME="RD02905ST-20">20</A>
Bingham PM, and
Zachar Z. inventors; PCT Int. Appl. WO 0024/734.
; Chem. Abstr. 2000, 132, 3081921
<A NAME="RD02905ST-21">21</A>
Yasuaki O. inventors; Jpn. KoKai Tokkyo Koho, JP 63,08,315.
; Chem. Abstr. 1988, 109, 196909qP
<A NAME="RD02905ST-22">22</A>
Kyotaro H. inventors; Jpn. KoKai Tokkyo Koho, JP 62,175,417.
; Chem. Abstr. 1988, 108, 62465nP
<A NAME="RD02905ST-23A">23a</A>
Kursanov DN.
Parnes ZN.
Loim NM.
Synthesis
1974,
633
<A NAME="RD02905ST-23B">23b</A>
Parnes ZN.
Bolestova GI.
Belenkiy LI.
Kursanov DN.
Izv. Akad. Nauk SSSR, Ser. Khim.
1973,
1918 ; Chem. Abstr. 1974, 80, 14800
<A NAME="RD02905ST-24">24</A>
Menon RB.
Ph. D. Thesis
University of Pune;
Maharashtra, India:
1987.
Data for Selected Compounds.
<A NAME="RD02905ST-25A">25a</A>
Methyl 4-(4-methoxycarbonyl-butyl)-2,2-dimethyl-5-oxo-(1,3)-dithiane-4-carboxylate
(8c): molecular formula: C14H22O5S2; yield 70%; viscous liquid. IR (CHCl3): 3021, 2953, 2925, 1748, 1713, 1439, 1160, 765 cm-1. 1H NMR (200 MHz, CDCl3 + CCl4): δ = 3.76 (d, J = 18.6 Hz, 1 H), 3.75 (s, 3 H), 3.60 (s, 3 H), 3.30 (d, J = 18.6 Hz, 1 H), 2.24 (t, J = 7.3 Hz, 2 H), 1.64-1.85 (m, 5 H), 1.72 (s, 3 H), 1.64 (s, 3 H), 1.17-1.27 (m, 2
H). 13C NMR (125 MHz, CDCl3 + CCl4): δ = 197.1 (s), 173.5 (s), 170.0 (s), 61.7 (s), 53.1 (q), 51.4 (q), 50.6 (s), 36.6
(t), 33.6 (t), 32.7 (q), 32.6 (t), 32.2 (q), 25.0 (t), 24.2 (t). MS (EI): m/z (%) = 334 (26), 303 (6), 270 (15), 260 (10), 237 (2), 228 (18), 212 (14), 197 (27),
180 (36), 169 (23), 159 (27), 155 (39), 141 (32), 127 (81), 123 (68), 115 (100), 99
(94), 87 (51), 73 (76), 59 (25). HRMS (ESI+ mode): m/z calcd for C14H22O5NaS2 [M + Na]+: 357.0806; found: 357.0811.
<A NAME="RD02905ST-25B">25b</A>
Methyl 5-[2,2-dimethyl-5-oxo-(1,3)-dithian-4-yl]pentanoate (9c): molecular formula: C12H20O3S2; yield 81%; viscous liquid. IR (CHCl3): 3020, 1732, 1711, 772, 744 cm-1. 1H NMR (200 MHz, CDCl3 + CCl4): δ = 3.98 (dd, J = 6.8, 5.9 Hz, 1 H), 3.64 (s, 3 H), 3.63 (d, J = 16.6 Hz, 1 H), 3.25 (d, J = 16.6 Hz, 1 H), 2.29 (t, J = 7.3 Hz, 2 H), 1.76-1.92 (m, 1 H), 1.84 (s, 3 H), 1.56-1.71 (m, 2 H), 1.66 (s, 3
H), 1.34-1.49 (m, 3 H). 13C NMR (125 MHz, CDCl3 + CCl4): δ = 204.0 (s), 173.6 (s), 51.4 (q), 50.4 (s), 47.1 (d), 37.1 (t), 33.7 (t), 32.8
(q), 31.9 (q), 27.2 (t), 26.6 (t), 24.7 (t). MS (EI): m/z (%) = 276 (57), 262 (3), 243 (13), 225 (6), 211 (8), 202 (11), 179 (8), 170 (100),
153 (24), 142 (28), 127 (36), 111 (16), 93 (21), 73 (68), 56 (11). HRMS (ESI+ mode): m/z calcd for C12H20O3NaS2 [M + Na]+: 299.0752; found: 299.0742.
<A NAME="RD02905ST-25C">25c</A>
5-[5-(p-Toluenesulfonyl)hydrazono-2,2-dimethyl-(1,3)-dithian-4-yl]pentanoic acid methyl ester
(2c): molecular formula: C19H28O4N2S3; yield 87%; white solid, mp 120 °C. IR (CHCl3): 3020, 2400, 1731, 757 cm-1. 1H NMR (200 MHz, CDCl3 + CCl4): δ = 8.53 (s, 1 H), 7.58 (d, J = 8.3 Hz, 2 H), 7.25 (d, J = 8.3 Hz, 2 H), 3.74 (dd, J = 7.8, 6.4 Hz, 1 H), 3.61 (s, 3 H), 3.56 (d, J = 15.6 Hz, 1 H), 3.21 (d, J = 15.6 Hz, 1 H), 2.37 (s, 3 H), 2.19 (t, J = 7.8 Hz, 2 H), 1.76-1.84 (m, 1 H), 1.68 (s, 3 H), 1.46 (s, 3 H), 1.20-1.61 (m, 5
H). 13C NMR (50 MHz, CDCl3 + CCl4): δ = 173.6 (s), 155.7 (s), 143.9 (s), 135.4 (s), 129.3 (d), 128.1 (d), 51.2 (q),
49.7 (s), 45.1 (d), 33.6 (t), 32.2 (q), 31.0 (q), 28.9 (t), 26.1 (t), 25.6 (t), 24.4
(t), 21.3 (q). MS (ESI, solvent: MeCN + H2O + CH3COONH4): m/z = 445.04 [M + 1]. HRMS (ESI+ mode): m/z calcd for C19H29N2O4S3 [M + H]+: 445.1289; found: 445.1271.
<A NAME="RD02905ST-26">26</A>
General Procedure for Decomposition of Tosylhydra-zones to Olefins.
A mixture of tosylhydrazone (1 mmol) and NaOH (2 mmol) in i-PrOH (10 mL) was refluxed for 2-3 h. The reaction was monitored by TLC, and after
the completion of the reaction, i-PrOH was removed under vacuum and the residue was extracted with Et2O. The ether layer was dried over anhyd Na2SO4 and filtered. Then Et2O was removed under vacuum and the residue was purified by column chromatography.
<A NAME="RD02905ST-27">27</A>
Typical Procedure for Entry 3 in Table 2 (3c and 4c). The mixture of tosylhydrazone 2c (200 mg, 0.450 mmol) and NaOH (40 mg, 2 mmol) in i-PrOH (10 mL) was refluxed for 2-3 h. The reaction was monitored by TLC and after
the completion of the reaction, i-PrOH was removed under vacuum and H2O was added to the reaction mixture. Then aqueous layer was washed with Et2O and then acidified with dilute HCl. Finally, the aqueous layer was extracted with
Et2O (3 × 15 mL). The ether layer was dried over anhyd Na2SO4, filtered and Et2O was removed under vacuum. The residue was purified by column chromatography to give
93 mg (84%) of pure product (3c and 4c).
Data for 5-(2,2-dimethyl-6H-[1,3]dithiin-4-yl)pentanoic acid(3c): molecular formula: C11H18O2S2; yield 84%; viscous liquid. IR (CHCl3): 2985, 1709, 1216, 1167 cm-1. 1H NMR (200 MHz, CDCl3 + CCl4): δ = 10.06 (br s, 1 H), 5.75 (t, J = 4.4 Hz, 1 H), 3.44 (d, J = 4.4 Hz, 2 H), 2.34 (t, J = 7.3 Hz, 2 H), 2.20 (t, J = 6.4 Hz, 2 H), 1.67 (s, 6 H), 1.42-1.74 (m, 4 H). 13C NMR (50 MHz, CDCl3 + CCl4): δ = 179.2 (s), 136.5 (s), 111.4 (d), 47.3 (s), 38.2 (t), 33.8 (t), 31.0 (q), 28.3
(t), 26.4 (t), 23.7 (t). MS (ESI, solvent: MeCN + H2O + CH3COONH4): m/z = 263.05 [M + NH3], 245.05 [M - 1].