References and Notes
<A NAME="RW13106ST-1A">1a</A>
Current Trends in Organic Synthesis
Scolastico C.
Nocotra F.
Plenum;
New York:
1999.
For recent reviews, see:
<A NAME="RW13106ST-1B">1b</A>
Li C.-J.
Chem. Rev.
2005,
105:
3095
<A NAME="RW13106ST-1C">1c</A>
Dilman AD.
Ioffe SL.
Chem. Rev.
2003,
103:
733
<A NAME="RW13106ST-1D">1d</A>
Fagnou K.
Lautens M.
Chem. Rev.
2003,
103:
169
<A NAME="RW13106ST-1E">1e</A> For a review on olefin metathesis, see:
Diver ST.
Giessert AJ.
Chem. Rev.
2004,
104:
1317
For a microreview on the reactions of 1,4-dilithio-1,3-dienes with carbonyl compounds,
see:
<A NAME="RW13106ST-2A">2a</A>
Xi Z.
Eur. J. Org. Chem.
2004,
2773
For selected examples, see:
<A NAME="RW13106ST-2B">2b</A>
Xi Z.
Song Q.
Chen J.
Guan H.
Li P.
Angew. Chem. Int. Ed.
2001,
40:
1913
<A NAME="RW13106ST-2C">2c</A>
Song Q.
Chen J.
Jin X.
Xi Z.
J. Am. Chem. Soc.
2001,
123:
10419
<A NAME="RW13106ST-3">3</A> For an example of the synthesis of dipyrromethane from α-alkylthiopyrrole and
benzaldehyde, see:
Thamyongkit P.
Bhise AD.
Taniguchi M.
Lindsey JS.
J. Org. Chem.
2006,
71:
903
<A NAME="RW13106ST-4">4</A>
Okauchi T.
Tanaka T.
Minami T.
J. Org. Chem.
2001,
66:
3924
<A NAME="RW13106ST-5">5</A>
Yin Y.-B.
Wang M.
Liu Q.
Hu J.-L.
Sun S.-G.
Kang J.
Tetrahedron Lett.
2005,
46:
4399
<A NAME="RW13106ST-6A">6a</A>
Kabalka GW.
Wu Z.
Ju Y.
Org. Lett.
2002,
4:
1491
<A NAME="RW13106ST-6B">6b</A>
Kabalka GW.
Wu Z.
Ju Y.
Org. Lett.
2002,
4:
3415
<A NAME="RW13106ST-6C">6c</A>
Yadav JS.
Reddy BVS.
Eeshwaraiah B.
Gupta MK.
Biswas SK.
Tetrahedron Lett.
2005,
46:
1161
<A NAME="RW13106ST-7">7</A>
Miranda PO.
Diaz DD.
Padron JI.
Ramirez MA.
Martin VS.
J. Org. Chem.
2005,
70:
57
<A NAME="RW13106ST-8A">8a</A>
Saito S.
Salter MM.
Gevorgyan V.
Tsuboya N.
Tando K.
Yamamoto Y.
J. Am. Chem. Soc.
1996,
118:
3970
<A NAME="RW13106ST-8B">8b</A>
Gevorgyan V.
Takeda A.
Homma M.
Sadayori N.
Radhakrishnan U.
Yamamoto Y.
J. Am. Chem. Soc.
1999,
121:
6391
<A NAME="RW13106ST-8C">8c</A>
Saito S.
Chounan Y.
Nogami T.
Fukushi T.
Tsuboya N.
Yamada Y.
Kitahara H.
Yamamoto Y.
J. Org. Chem.
2000,
65:
5350
<A NAME="RW13106ST-9A">9a</A>
Hansen EC.
Lee D.
Org. Lett.
2004,
6:
2035
<A NAME="RW13106ST-9B">9b</A>
Kang B.
Kim D.-H.
Do Y.
Chang S.
Org. Lett.
2003,
5:
3041
<A NAME="RW13106ST-10">10</A>
Hayes ME.
Shinokubo H.
Danheiser RL.
Org. Lett.
2005,
7:
3917
<A NAME="RW13106ST-11A">11a</A>
Saito S.
Tanaka T.
Koizumi T.
Tsuboya N.
Itagaki H.
Kawasaki T.
Endo S.
Yamamoto Y.
J. Am. Chem. Soc.
2000,
122:
1810
<A NAME="RW13106ST-11B">11b</A>
Treitel N.
Eshdat L.
Sheradsky T.
Donovan PM.
Tykwinski RR.
Scott LT.
Hopf H.
Rabinovitz M.
J. Am. Chem. Soc.
2006,
128:
4703
Reviews:
<A NAME="RW13106ST-12A">12a</A>
Dieter RK.
Tetrahedron
1986,
42:
3029
<A NAME="RW13106ST-12B">12b</A>
Junjappa H.
Tla H.
Asokan CV.
Tetrahedron
1990,
46:
5423
<A NAME="RW13106ST-12C">12c</A>
Tla H.
Junjappa H.
Barun O.
J. Organomet. Chem.
2001,
624:
34
<A NAME="RW13106ST-12D">12d</A>
Elgemeie GH.
Sayed SH.
Synthesis
2001,
1747
For selected examples, see:
<A NAME="RW13106ST-13A">13a</A>
Bi X.
Dong D.
Liu Q.
Pan W.
Zhao L.
Li B.
J. Am. Chem. Soc.
2005,
127:
4578
<A NAME="RW13106ST-13B">13b</A>
Kang J.
Liang F.
Sun S.-G.
Liu Q.
Bi X.-H.
Org. Lett.
2006,
8:
2547
<A NAME="RW13106ST-13C">13c</A>
Ouyang Y.
Dong D.
Yu H.
Liang Y.
Liu Q.
Adv. Synth. Catal.
2006,
348:
206
<A NAME="RW13106ST-13D">13d</A>
Zhao L.
Liang F.
Bi X.
Sun S.
Liu Q.
J. Org. Chem.
2006,
71:
1094
<A NAME="RW13106ST-13E">13e</A>
Dong DW.
Bi X.
Liu Q.
Cong FD.
Chem. Commun.
2005,
28:
3580
<A NAME="RW13106ST-13F">13f</A>
Bi X.
Dong D.
Li Y.
Liu Q.
J. Org. Chem.
2005,
70:
10886
<A NAME="RW13106ST-14">14</A>
Dong D.
Liu Y.
Zhao Y.-L.
Qi Y.
Wang Z.
Liu Q.
Synthesis
2005,
85
<A NAME="RW13106ST-15A">15a</A>
Zhao Y.-L.
Liu Q.
Zhang J.-P.
Liu Z.-Q.
J. Org. Chem.
2005,
70:
6913
<A NAME="RW13106ST-15B">15b</A>
Zhao Y.-L.
Zhang W.
Zhang J.-Q.
Liu Q.
Tetrahedron Lett.
2006,
47:
3157
<A NAME="RW13106ST-16">16</A>
Zhao Y.-L.
Liu Q.
Zhang Y.-F.
Sun S.-G.
Li Y.-N.
Synlett
2006,
231
<A NAME="RW13106ST-17">17</A>
Preparation of Compounds 3 (3ae as example); Typical Procedure: To a stirred solution of enyne 1a (2.0 mmol, 428 mg) and 4-nitrobenzaldehyde (2e; 1.0 mmol, 151 mg) in anhyd CH2Cl2 (20 mL) cooled to 0 °C in an ice bath, TiCl4 (1.0 mmol, 0.11 mL) was added dropwise by syringe within 3 min under a nitrogen atmosphere.
Then the reaction mixture was stirred for 1 h at 0 °C. After 1a was consumed (monitored by TLC), the reaction mixture was poured into a sat. NaHCO3 solution (50 mL) and extracted with CH2Cl2 (2 × 10 mL). The combined organic extracts were dried over anhyd MgSO4, filtered and concentrated under reduced pressure to yield the corresponding crude
product, which was purified by silica gel chromatography (Et2O-hexane = 1:1) to give 3ae (444 mg, 70%) as a white crystal.
(3
Z
,6
E
)-Dimethyl 3,7-Dichloro-2,8-di(1,3-dithian-2-ylidene)-5-(4-nitrophenyl)nona-3,6-dienedioate
(
3ae): white crystalline solid; mp 184-186 °C. 1H NMR (500 MHz, CDCl3): δ = 2.15-2.20 (m, 4 H), 2.92-2.96 (m, 8 H), 3.60 (br s, 3 H), 3.75 (s, 3 H), 4.70
(t, J = 9.5 Hz, 1 H), 5.70 (d, J = 9.5 Hz, 1 H), 6.00 (d, J = 9.5 Hz, 1 H), 7.50 (d, J = 8.5 Hz, 2 H), 8.15 (q, J = 8.5 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 23.48 (2 × C), 29.38 (2 × C), 29.51, 29.92, 45.63 (2 × C), 52.20, 123.33 (2
× C), 123.81 (2 × C), 128.91 (2 × C), 131.75, 132.57, 146.98 (2 × C), 163.98 (2 ×
C), 164.23 (2 × C), 164.66 (2 × C). IR (KBr): 1009, 1193, 1253, 1346, 1493, 1518,
1694, 2946, 3445 cm-1. MS (EI): m/z = 657 [M + 23]+. Anal. Calcd for C25H25Cl2NO6S4: C, 47.31; H, 3.97; N, 2.21. Found: C, 47.50; H, 3.82; N, 2.03.
(3
Z
,6
E
)-Dimethyl 3,7-Dichloro-2,8-di(1,3-dithian-2-ylidene)-5-phenylnona-3,6-dienedioate
(
3aa): white crystalline solid; mp 168-170 °C. 1H NMR (500 MHz, CDCl3): δ = 2.13-2.19 (m, 4 H), 2.89-3.00 (m, 8 H), 3.58 (br s, 3 H), 3.72 (s, 3 H), 4.62
(t, J = 9.5 Hz, 1 H), 5.73 (d, J = 9.0 Hz, 1 H), 6.11 (d, J = 9.0 Hz, 1 H), 7.19-7.22 (m, 1 H), 7.28-7.31 (m, 4 H). 13C NMR (125 MHz, CDCl3): δ = 23.20 (2 × C), 29.04 (2 × C), 29.16, 29.52, 45.43 (2 × C), 51.77, 123.51 (2
× C), 126.62 (2 × C), 127.63 (2 × C), 128.24 (2 × C), 132.91, 133.80, 163.70 (2 ×
C), 163.73 (2 × C), 164.17 (2 × C). IR (KBr): 742, 859, 1007, 1145, 1256, 1494, 1692,
2943, 3443 cm-1. MS (EI): m/z = 589 [M + 1]+. Anal. Calcd for C25H26Cl2O4S4: C, 50.92; H, 4.44. Found: C, 51.11;
H, 4.60.
(3
Z
,6
E
)-Dimethyl 5-(Benzo[
d
][1,3]dioxol-5-yl)-3,7-dichloro-2,8-di(1,3-dithian-2-ylidene)nona-3,6-dienedioate
(
3ab): white crystalline solid; mp 172-174 °C. 1H NMR (500 MHz, CDCl3): δ = 2.16-2.19 (m, 4 H), 2.94-2.95 (m, 8 H), 3.68 (br s, 3 H), 3.75 (s, 3 H), 4.53
(t, J = 9.5 Hz, 1 H), 5.68 (d, J = 9.0 Hz, 1 H), 5.92 (s, 2 H), 6.03 (d, J = 9.5 Hz, 1 H), 6.72 (d, J = 8.5 Hz, 1 H), 6.77 (d, J = 8.5 Hz, 1 H), 6.86 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 23.07, 23.19, 29.03, 29.16, 29.37, 29.52, 44.95, 51.53, 51.76, 100.84, 107.89,
108.10, 108.17, 108.27, 120.32, 120.54, 123.38, 128.21, 128.85, 132.98, 133.31, 133.64,
145.93, 147.56, 163.75, 164.08. IR (KBr): 2924, 2853, 1695, 1506, 1457, 1436, 1252
cm-1. MS (EI): m/z = 655 [M + 23]+. Anal. Calcd for C26H26Cl2O6S4: C, 49.28; H, 4.14. Found: C, 49.38; H, 4.23.
(3
Z
,6
E
)-Dimethyl 3,7-Dichloro-2,8-di(1,3-dithian-2-ylidene)-5-(4-methoxyphenyl)nona-3,6-dienedioate
(
3ac): white crystalline solid; mp 170-172 °C. 1H NMR (500 MHz, CDCl3): δ = 2.13-2.19 (m, 4 H), 2.92-2.95 (m, 8 H), 3.62-3.74 (br s, 3 H), 3.74 (s, 3 H),
3.77 (s, 3 H), 4.56 (t, J = 9.0 Hz, 1 H), 5.70 (d, J = 9.0 Hz, 1 H), 6.07 (d, J = 9.0 Hz, 1 H), 6.82 (d, J = 8.5 Hz, 2 H), 7.23 (d, J = 8.5 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 23.54 (2 × C), 29.37 (2 × C), 29.50, 29.86, 44.95, 52.11 (2 × C), 55.51, 113.90
(2 × C), 123.90 (2 × C), 128.95 (2 × C), 133.53, 134.35, 158.53 (2 × C), 163.97 (2
× C), 164.12 (2 × C), 164.52 (2 × C). IR (KBr): 1010, 1193, 1255, 1464, 1508, 1644,
1691, 2925, 3443 cm-1. MS (EI): m/z = 641 [M + 23]+. Anal. Calcd for C26H28Cl2O5S4: C, 50.39; H, 4.55. Found: C, 50.18; H, 4.51.
(3
Z
,6
E
)-Dimethyl 3,7-Dichloro-2,8-di(1,3-dithian-2-ylidene)-5-(p
-tolyl)nona-3,6-dienedioate (
3ad): white crystalline solid; mp 178-180 °C. 1H NMR (500 MHz, CDCl3): δ = 2.15-2.20 (m, 4 H), 2.31 (s, 3 H), 2.92-2.97 (m, 8 H), 3.62 (br s, 3 H), 3.75
(s, 3 H), 4.58 (t, J = 9.0 Hz, 1 H), 5.72 (d, J = 8.5 Hz, 1 H), 6.08 (d, J = 9.0 Hz, 1 H), 7.09 (d, J = 8.0 Hz, 2 H), 7.16 (d, J = 8.0 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 20.99, 23.23, 29.06, 29.17, 29.35, 29.54, 30.91, 45.08 (2 × C), 51.77, 123.60,
127.36, 127.51, 128.68, 128.96, 129.13, 133.20, 133.52, 133.95, 136.15, 163.58 (2
× C), 163.79 (2 × C), 164.21 (2 × C). IR (KBr): 1008, 1190, 1251, 1505, 1692, 2856,
2923, 3442 cm-1. MS (EI): m/z = 603 [M + 1]+. Anal. Calcd for C26H28Cl2O4S4: C, 51.73; H, 4.68. Found: C, 51.90; H, 4.80.
(3
Z
,6
E
)-Dimethyl 3,7-Dichloro-2,8-di(1,3-dithian-2-ylidene)-5-(thiophen-2-yl)nona-3,6-dienedioate
(
3af): white crystalline solid; mp 179-180 °C. 1H NMR (500 MHz, CDCl3): δ = 2.15-2.20 (m, 4 H), 2.93-2.99 (m, 8 H), 3.72 (br s, 3 H), 3.75 (s, 3 H), 4.80
(t, J = 9.0 Hz, 1 H), 5.73 (d, J = 8.0 Hz, 1 H), 6.06 (d, J = 9.5 Hz, 1 H), 6.94 (q, J = 6.0 Hz, 2 H), 7.18 (d, J = 6.0 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 23.21 (2 × C), 29.05, 29.19, 29.45, 30.90, 41.46 (2 × C), 51.77, 123.30 (2
× C), 124.41 (2 × C), 124.58, 126.63, 132.31, 132.82, 163.72 (2 × C), 163.90 (2 ×
C), 164.13 (2 × C). IR (KBr): 853, 1008, 1194, 1254, 1433, 1493, 1692, 2945 cm-1. MS (EI): m/z = 617 [M + 23]+.
(3
Z
,6
E
)-Dimethyl 3,7-Dichloro-5-(4-chlorophenyl)-2,8-di(1,3-dithian-2-ylidene)nona-3,6-dienedioate
(
3ag): white crystalline solid; mp 142-144 °C. 1H NMR (500 MHz, CDCl3): δ = 2.15-2.20 (m, 4 H), 2.93-2.95 (m, 8 H), 3.60 (br s, 3 H), 3.75 (s, 3 H), 4.58
(t, J = 9.5 Hz, 1 H), 5.69 (d, J = 9.0 Hz, 1 H), 6.06 (d, J = 9.0 Hz, 1 H), 7.27 (m, 4 H). 13C NMR (125 MHz, CDCl3): δ = 23.20 (2 × C), 29.06 (2 × C), 29.19, 29.56, 44.84 (2 × C), 51.81, 123.34 (2
× C), 128.35 (2 × C), 128.53 (2 × C), 129.05, 132.43, 133.34 (2 × C), 163.66 (2 ×
C), 163.92 (2 × C), 164.08 (2 × C). IR (KBr): 1011, 1195, 1258, 1460, 1258, 1496,
1693, 2861, 2926, 3441 cm-1. MS (EI): m/z = 645 [M + 23]+.
(3
Z
,6
E
)-Dimethyl 3,7-Dichloro-2,8-di(1,3-dithian-2-ylidene)-5-(4-fluorophenyl)nona-3,6-dienedioate
(
3ah): white crystalline solid; mp 144-146 °C. 1H NMR (500 MHz, CDCl3): δ = 2.15-2.16 (m, 4 H), 2.78-2.92 (m, 8 H), 3.61 (br s, 3 H), 3.73 (s, 3 H), 4.58
(t, J = 9.5 Hz, 1 H), 5.68 (d, J = 9.0 Hz, 1 H), 6.06 (d, J = 9.0 Hz, 1 H), 6.96 (t, J = 8.5 Hz, 2 H), 7.26 (d, J = 8.5 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 23.21 (2 × C), 29.06, 29.18, 29.39, 29.55, 44.71 (2 × C), 51.78, 114.94, 115.11,
123.42 (2 × C), 129.13 (2 × C), 129.19 (2 × C), 132.67, 133.64, 160.63 (2 × C), 162.58,
163.67, 163.74, 164.09. IR (KBr): 2949, 1689, 1508, 1487, 1250, 1219, 1158, 916 cm-1. MS (EI): m/z = 607 [M + 1]+.
(3
Z
,6
E
)-Dimethyl 3,7-Dichloro-2,8-di(1,3-dithian-2-ylidene)-5-[(
E
)-styryl]nona-3,6-dienedioate (
3ai): white solid; mp 220-222 °C. 1H NMR (500 MHz, CDCl3): δ = 2.16-2.19 (m, 4 H), 2.95-2.96 (m, 8 H), 3.72 (br s, 3 H), 3.75 (s, 3 H), 4.18
(q, J = 8.5 Hz, 1 H), 5.60 (d, J = 9.0 Hz, 1 H), 5.93 (d, J = 9.0 Hz, 1 H), 6.08 (d, J = 10 Hz, 1 H), 6.49 (d, J = 10 Hz, 1 H), 7.20-7.23 (m, 1 H), 7.28-7.33 (m, 4 H). 13C NMR (125 MHz, CDCl3): δ = 23.25 (2 × C), 29.13, 29.38, 29.58, 30.88, 43.64 (2 × C), 51.78, 109.69, 123.61,
126.17 (2 × C), 127.31 (2 × C), 127.74, 128.44 (2 × C), 130.66, 132.64 (2 × C), 137.18
(2 × C), 163.78 (2 × C), 164.14 (2 × C). IR (KBr): 876, 1009, 1196, 1255, 1452, 1692,
2990, 3444 cm-1. MS (EI): m/z = 615 [M + 1]+. Anal. Calcd for C27H28Cl2O4S4: C, 52.67; H, 4.58. Found: C, 52.93; H, 4.80.
(3
Z
,6
E
)-Dimethyl 5-(Benzo[d][1,3]dioxol-5-yl)-3,7-dibromo-2,8-di(1,3-dithian-2-ylidene)nona-3,6-dienedioate
(
3aj): white crystalline solid; mp 178-180 °C. 1H NMR (500 MHz, CDCl3): δ = 2.19-2.23 (m, 4 H), 2.96-3.05 (m, 8 H), 3.68 (br s, 3 H), 3.78 (s, 3 H), 4.48
(t, J = 9.5 Hz, 1 H), 5.83 (d, J = 9.0 Hz, 1 H), 5.91 (s, 2 H), 6.27 (q, J = 9.0 Hz, 1 H), 6.74 (d, J = 8.0 Hz, 1 H), 6.79 (d, J = 8.0 Hz, 1 H), 6.89 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 23.31, 23.55, 29.30, 29.35, 29.59, 29.85, 48.75, 49.06, 52.04, 101.14, 108.22,
108.44, 108.58, 108.67, 120.74, 120.95, 121.06, 125.27, 133.51, 133.92, 136.25, 136.42,
146.54, 148.03, 163.54, 164.41. IR (KBr): 1184, 1209, 1413, 1560, 1607, 1687, 2987
cm-1. MS (EI): m/z = 721 [M + 1]+.
(3
Z
,6
E
)-Dimethyl 5-(Benzo[d][1,3]dioxol-5-yl)-3,7-dichloro-2,8-di(1,3-dithiolan-2-ylidene)nona-3,6-dienedioate
(
3bb): white crystalline solid; mp 192-194 °C. 1H NMR (500 MHz, CDCl3): δ = 3.34-3.49 (m, 8 H), 3.71 (br s, 3 H), 3.77 (s, 3 H), 4.60 (t, J = 9.5 Hz, 1 H), 5.76 (d, J = 9.0 Hz, 1 H), 5.95 (s, 2 H), 6.07 (d, J = 9.0 Hz, 1 H), 6.74 (q, J = 8.0 Hz, 2 H), 6.90 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 37.10 (2 × C), 39.86 (2 × C), 45.09 (2 × C), 52.29, 101.19, 108.28, 108.51,
111.72, 115.55, 120.73, 130.11, 130.61, 133.02, 133.91, 146.53, 147.96, 165.00, 165.33
(2 × C), 168.41, 170.13. IR (KBr): 934, 1040, 1194, 1249, 1433, 1507, 1685, 2947,
3649 cm-1. MS (EI): m/z = 605 [M + 1]+. Anal. Calcd for C24H22Cl2O6S4: C, 47.60; H, 3.66. Found: C, 47.76; H, 3.79.
(3
Z
,6
E
)-Dimethyl 3,7-Dichloro-2,8-di(1,3-dithiolan-2-ylidene)-5-(4-nitrophenyl)nona-3,6-dienedioate
(
3be): white crystalline solid; mp 213-215 °C. 1H NMR (500 MHz, CDCl3): δ = 3.36-3.66 (m, 8 H), 3.66 (br s, 3 H), 3.77 (s, 3 H), 4.74 (t, J = 9.5 Hz, 1 H), 5.80 (d, J = 9.5 Hz, 1 H), 6.05 (d, J = 9.5 Hz, 1 H), 7.48 (d, J = 8.5 Hz, 2 H), 8.16 (d, J = 8.5 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 36.79, 36.92, 39.66 (2 × C), 45.22 (2 × C), 52.13, 114.86 (2 × C), 123.62 (2
× C), 128.52 (2 × C), 131.00, 131.43, 146.79 (2 × C), 164.49 (2 × C), 164.83 (2 ×
C), 168.58 (2 × C). IR (KBr): 1013, 1196, 1248, 1266, 1347, 1435, 1516, 1685, 2948,
3446 cm-1. MS (EI): m/z = 628 [M + 23]+.
<A NAME="RW13106ST-18">18</A>
Crystal data for 3ae: C25H25Cl2NO6S4; white crystal, M = 634.60, monoclinic, P21/n, a = 11.241 (7) Å, b = 13.167 (8) Å, c = 19.679 (9) Å, α = 90.00°, β = 95.203(12)°, γ = 90.00°, V = 2901 (3) Å3, Z = 4, T = 293 (2) K, F000 = 1312, R
1 = 0.0739, wR
2 = 0.1462. The CCDC deposition number is 293614.
<A NAME="RW13106ST-19">19</A>
Yahiro S.
Shibata K.
Saito T.
Okauchi T.
Minami T.
J. Org. Chem.
2003,
68:
4947
<A NAME="RW13106ST-20A">20a</A>
Liu Q.
Che G.
Yu H.
Liu Y.
Zhang J.
Zhang Q.
Dong DW.
J. Org. Chem.
2003,
68:
9148
<A NAME="RW13106ST-20B">20b</A>
Dong D.
Ouyang Y.
Yu H.
Liu Q.
Liu J.
Wang M.
Zhu J.
J. Org. Chem.
2005,
70:
4535
<A NAME="RW13106ST-21">21</A>
Synthesis of Compounds 4 (4ab as example); Typical Procedure: To a stirred solution of compound 3ab (1.0 mmol, 633 mg) in EtOH (15 mL) was added HCl (0.5 mmol, 0.043 mL) in one portion.
Then the reaction mixture was heated to the reflux temperature for 1 h. After 3ab was consumed (monitored by TLC), the reaction mixture was poured into H2O (50 mL) and extracted with Et2O (3 × 10 mL). The combined organic extracts were dried over anhyd MgSO4, filtered and concentrated under reduced pressure to yield the corresponding crude
product, which was purified by chromatography over silica gel column using Et2O-hexane (1:2) as eluent to give 4ab (417 mg, 70%) as a white crystal.
Dimethyl 5-(Benzo[d][1,3]dioxol-5-yl)-2,8-di(1,3-dithian-2-ylidene)-3,7-dioxononanedioate
(
4ab): white crystalline solid; mp 124-126 °C. 1H NMR (500 MHz, CDCl3): δ = 2.16-2.22 (m, 4 H), 2.76-2.79 (m, 4 H), 2.80 (d, J = 8.0 Hz, 1 H), 2.83 (d, J = 8.0 Hz, 1 H), 2.89-2.92 (m, 4 H), 2.93 (d, J = 6.5 Hz, 1 H), 2.96 (d, J = 6.5 Hz, 1 H), 3.68 (dd, J = 6.5, 8.0 Hz, 1 H), 3.80 (s, 6 H), 5.88 (s, 2 H), 6.64-6.67 (m, 3 H). 13C NMR (125 MHz, CDCl3): δ = 23.85 (2 × C), 29.16 (2 × C), 29.35 (2 × C), 37.24 (2 × C), 47.95, 52.04 (2
× C), 100.66, 107.94, 108.06, 120.68, 127.52, 137.34, 145.80, 147.25 (2 × C), 165.21
(2 × C), 169.53 (2 × C), 195.17 (2 × C). IR (KBr): 932, 1039, 1247, 1457, 1488, 1506,
1653, 1698, 3446 cm-1. MS (EI): m/z = 597 [M + 1]+. Anal. Calcd for C26H28O8S4: C, 52.33; H, 4.73. Found: C, 52.51; H, 4.88.
Dimethyl 2,8-Di(1,3-dithian-2-ylidene)-3,7-dioxo-5-
para
-tolylnonanedioate (
4ad): white crystalline solid; mp 119-121 °C. 1H NMR (500 MHz, CDCl3): δ = 2.16-2.21 (m, 4 H), 2.27 (s, 3 H), 2.74-2.77 (m, 4 H), 2.80 (d, J = 7.0 Hz, 1 H), 2.84 (d, J = 7.0 Hz, 1 H), 2.85-2.91 (m, 4 H), 2.97 (d, J = 7.0 Hz, 1 H), 2.99 (d, J = 7.0 Hz, 1 H), 3.71 (t, J = 7.0 Hz, 1 H), 3.79 (s, 6 H), 7.03 (d, J = 8.0 Hz, 2 H), 7.06 (d, J = 8.0 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 21.27 (2 × C), 24.16, 29.30 (4 × C), 37.35 (2 × C), 48.24, 52.33 (2 × C), 120.77,
127.85, 129.14 (2 × C), 129.28, 135.92, 140.69 (2 × C), 165.48 (2 × C), 169.53 (2
× C), 195.79
(2 × C).
IR (KBr): 816, 1074, 1247, 1439, 1469, 1659, 1697, 2946 cm-1. MS (EI): m/z = 567 [M + 1]+.
<A NAME="RW13106ST-22A">22a</A>
Koskinen AMP.
Karisalmi K.
Chem. Soc. Rev.
2005,
34:
677
<A NAME="RW13106ST-22B">22b</A>
Staunton J.
Wilkinson B.
Chem. Rev.
1997,
97:
2611
<A NAME="RW13106ST-23A">23a</A>
Kabalka GW.
Yao M.-L.
Borella S.
Wu Z.-Z.
Org. Lett.
2005,
7:
2865
<A NAME="RW13106ST-23B">23b</A>
Kabalka GW.
Wu Z.
Ju Y.
Yao M.-L.
J. Org. Chem.
2005,
70:
10285
<A NAME="RW13106ST-23C">23c</A>
Kabalka GW.
Yao M.-L.
Borella S.
Wu Z.
Chem. Commun.
2005,
2492
