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Please login to access the full content or check if you have access via9.10.1.4.2.1 Method 1: Substitution Reactions Involving Organostannanes (The Stille Reaction)
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Schatz, J., Science of Synthesis, (2001) 9, 370.
Palladium-catalyzed cross coupling of intermediate (trialkylstannyl)thiophenes[841,842] with aryl, acyl, alk-1-enyl, or allyl halides or triflates,[843] as well as with terminal alkynes, is an effective way for the synthesis of the corresponding thiophene derivatives. The reaction proceeds through a three-step catalytic cycle following the general scheme of metal-assisted cross-coupling reactions. Oxidative addition, transmetalation, and reductive elimination are key steps in the catalytic cycle. The active catalyst is believed to be a palladium(0) species formed in situ from palladium complexes like tetrakis(triphenylphosphine)palladium(0), dichlorobis(triphenylphosphine)palladium(II), or similar.[844–851] Addition of a co-catalyst such as copper(I) salts can enhance the Stille coupling.[852–855] The reactivity of the halides used for the cross-coupling reaction decreases in the sequence R1I > R1Br > R1Cl. Furthermore, the reaction is usually performed in solvents such as tetrahydrofuran, dioxane, dimethylformamide, or 1-methylpyrrolidin-2-one under basic conditions (trialkylamine, lithium carbonate, sodium carbonate, or pyridine) (Scheme 103).[855,856,858,859] The Stille coupling is a good choice for the synthesis of mixed aryl–thienyl oligomers as well as of bi- and terthiophenes.[61,558,860–873]
Meeeee 888 Meeeee Meeeeeee ee 8-(Meeeeeeeeeeeeee)eeeeeeeeee[888,888–888]
M8 | M8Mee | Meeee (%) | Mee |
---|---|---|---|
Me | 88 | [888] | |
Me | (M)-MeM8MMM=MMM | 88 | [888] |
Me | 8-eeeeeeeeeeeee | 88 | [888] |
Me | 88 | [888] | |
Me | 88 | [888] | |
Me | (M)-MeMM=MMMMMe | 88 | [888] |
Me | M8M=MMMM8Me | 88 | [888] |
Me | 8-MeM8M8M | 88 | [888] |
Meeeeeeeeeee Meeeeeeee
8-(8-Meeeeeeeeeee)eeeeeeeee (888, M8 = 8-MeM8M8):[888]
Meeeeeeee eeee (Meeeeeeeee; Meee–Meeeeee, Meeeeee Meeeeeeee), Meeeeeeee (8888), e 888, eeee eeeeeeeeee eeee Meee Meeee&Meee, Mee.
M 888-eM, eeeee-eeeee Meeeeee eeeee eee eeeeee eeee M8 eee eeeeeee eeee 8-MeM8M8M (88.8 e, 88.8 eeee), MeM (888 ee, 8.88 eeee), Me8Me (8.8 e, 8.88 eeee), eee eeeee MMM (888 eM). Mee eeee eeee eee eeeeeeee eee 88 eee eee eeee 8-(eeeeeeeeeeeeeee)eeeeeeeee (88.8 eM, 88.8 eeee) eee eeeee. Mee eeeeeeee eeeee eee eeeeeeeee ee e eeee eeeeeeeee ee 88°M eee 88% Me/M (888 ee, 8.8 eeee) eee eeeee. Mee eeeeeee eee eeee ee 88°M eee 88 e eeeee M8 eee eeee eeeeeee ee eeee ee 88°M eee eeeeeee eeee MeMMe (888 eM). Mee eeee eeeeeee eee eeeeee eeee ee eee. MeM (888 eM) eee eeeeeee eeeeeeeeee eee 88 eee. Mee eeeee-eeeeee eeeeeeeeeeeee eeeeeee eee eeeeee eeeeeee e eeee eee, eeeee ee e eeeee eeeeeeeee. Mee eeeeeeee eee eeeeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee MeMMe (8 × 888 eM). Mee eeeeeee eeeeeeee eeee eeeeeeee eee eeeeeee eeee eeeeeee eee. MeM eee 88 eee. Mee eeeeeee eee eeeeee eeeee eeeeeee e eee ee eeee. Mee eee eee eeeeee eeee MeMMe (88 eM). Mee eeeeeee eee eeeeeeeeeee eeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeee eeeeee eeee eeeeee eeee M8M (8 × 888 eM) eee eeeee (888 eM). Mee eeee eeeeee eeee eee eeeee (MeMM8) eee eeeeeeee. Mee eeee MeMM8 eee eeeeee eeee MeMMe (88 eM). Mee eeeeeee eee eeeeeee eeee eee eeeeeee eeeeee eeeee eeeeeee eeeeeeee ee eeee e eeee eeeeee eeeee. MMMM (eeeeee eee, eeeeee/MM8Me8 eeeeeeee) eeee eee eeeeeee; eeeee: 8.88 e (88%); ee 888–888°M.
References
[61] | Me, M. M.; Me, M.; Meee, M. M. M., Meeeeee Mee./Meee., (8888), 888. |
[558] | Meeeee, M.; Meeeeee, M.; Meeee, M. M., Meeeeeeeeee, (8888) 88, 88888. |
[841] | Meeee, M.; Meeeeee, M.; Meeeeeee, M., M. Meeeeeeeee. Meee., (8888) 88, 8888. |
[842] | Meeeeeeee, M. M., Meeeeeeeeee, (8888) 88, 888. |
[843] | Meeee, M. M.; Meeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[844] | Meeeeee, M. M., Meeee. Meeee., (8888) 88, 888. |
[845] | Meeeeeeee, M. M.; Mee, M. M. M.; Meeee, M. M., M. Meee. Mee. M, (8888), 8888. |
[846] | Meeeeee, M. M.; Meeeee, M. M.; Meee, M. M., M. Me. Meee. Mee., (8888) 88, 888. |
[847] | Meeeeeeeee, M.; Meeeeeeeee, M.; Meee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[848] | Meeeeee, M. M.; Meeeee, M. M. M. M. M.; Meeeeeeee, M., Meeee. Meee., (8888) 88, 8888. |
[849] | Meeeee, M.; MeMeee, M. M.; Meee, M. M., Meee. Meeeee., (8888), 888. |
[850] | Meeeeee, M.; Meeeeee, M.; Meeeee, M.; Meeeee, M.; Meeeeee, M.; Meeeeee, M., M. Me. Meee. Mee., (8888) 888, 888. |
[851] | Meee, M. M.; Meee, M.; Meeeeeeee, M., M. Meee. Mee., (8888), 8888. |
[852] | Meeeeeeeee, M. M.; Meee-Meeeeee, M., Mee. Meeee., (8888) 88, 888. |
[853] | Meeeeeeeee, M. M.; Meeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[854] | Meeeeeeeee, M. M.; Meeeee, M.; Meeeeee, M.; Meeeeeee, M.; Meee, M., M. Mee. Meee., (8888) 88, 8888. |
[855] | Meeeee, M., Meee Meee. Meee., (8888) 88, 88. |
[856] | Meeeeeeeeee, M.; Meeeeeeee, M. M. M.; Meeeeee, M. M.; Meeeeeee, M. M. M.; Meeeee, M. M., Meeee. Mee., (8888) 88, 888. |
[858] | Meeeeeee, M. M., Me Meeee-Meeeeeeee Meeee-Meeeeeee Meeeeeeee, Meeeeeeee, M.; Meeee, M. M., Mee.; Meeee-MMM: Meeeeeee, (8888); e 888. |
[859] | Meeeee, M.; Meeeeeeeeeeee, M. M. M. M., Mee. Meeee. (M. M.), (8888) 88, 8. |
[860] | Meeeeeee, M.; Meeeeeee, M., Meee. Meee. Meee, (8888) 88, 888. |
[861] | Meee, M.-M.; Mee, M.-M.; Meee, M.-M., M. Mee. Meee., (8888) 88, 8888. |
[862] | Meeeeeee, M.; Meeeeee, M.; Meeeeee, M.; Meeee, M.; Meeeeeeee, M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 8888. |
[863] | Meeee, M. M.; Möeeeeeee, M.-M.; Meeeeeeee, M., M. Meeeeeeeee. Meee, (8888) 88, 888. |
[864] | Meeee, M. M.; Möeeeeeee, M.-M.; Meeeeeeee, M., M. Meeeeeeeee. Meee, (8888) 88, 888. |
[865] | Meeee, M.; Meee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[866] | Mee, M. M.; Meee, M. M.; Me, M. M., Meee. Meeee., (8888) 8, 8. |
[867] | Meeee, M. M.; Mee, M. M.; Meeeee, M. M.; Meeeeee, M. M., Meeee. Meeeee., (8888) 88, 888. |
[868] | Meeeeeeeee, M.; Meeeeeeeee, M., Meeeeeeeeee, (8888) 88, 88888. |
[869] | Meeee, M.; Meeeeee, M.; Meeeeee, M., Meeee. Meeeee., (8888) 88, 8888. |
[870] | Mäeeeee, M.; Meee, M.; Meeee, M.; Müeeeeee, M.; Meeee, M. M.; Meee, M. M.; Meeeeee, M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 888. |
[871] | Meeeeeeee, M.; Möeeeeeee, M.-M., Meee Meee. Meeee., (8888) 88, 888. |
[872] | Meeeeeeeee, M.; Meeeeeeeee, M.; Meeeee, M.; Meeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[873] | Meeeeeeee, M.; Meeeee, M., Meeeeeeeeeee, (8888) 88, 888. |
[874] | Meeeeeeeee, M. M.; Meee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[875] | Meeee, M.; Meeeeee, M.; Meeeeee, M.; Meeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[876] | Meeee, M. M., Meeee. Meeeee., (8888) 88, 888. |
[877] | Meee, M.; Meöee, M.; Meeeeeeee, M.; Möeeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[878] | Meee, M.; Mee, M.; Me, M.; Mee, M., Meeeee Meeeee, (8888) 88, 888; Meee. Meeee., (8888) 888, 888888. |
[879] | Meeeeee, M. M.; Meeeeeee, M. M.; Meeeeeeeee, M. M., Meee. Meee. Meee MMMM, (8888) 888, 888; Meee. Meeee., (8888) 88, 888888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 8e, 888.