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All 2 posts Subject: Indole 3-alkylation Please login to post Down

Rhodium
(Chief Bee)
09-28-03 00:47
No 461398
User Picture       Indole 3-alkylation
(Rated as: good read)

For example, 2-dimethylaminoethanal would give DMT, and alpha-bromo-acetaldehyde would give 3-(2-bromoethyl)-indole, which in turn would be ready for alkylation by any dialkylamine to give the corresponding N,N-dialkyltryptamine.

A general method for C3 reductive alkylation of indoles
Anu Mahadevan,Howard Sarda, Mario Gonzalez, John C. McKew
Tetrahedron Letters 44(24), 4589-4591 (2003) (https://www.rhodium.ws/pdf/reductive.3-alkylation.indoles.pdf)
DOI:10.1016/S0040-4039(03)01010-4

Abstract

General indole C₃ reductive alkylation conditions have been developed. The scope of this reaction includes C₂ unsubstituted indoles, aryl and alkyl aldehydes, as well as N–H and N-alkyl indole substrates.

Rhodium
(Chief Bee)
10-15-04 01:11
No 535894
User Picture       Pd-catalyzed 3-nitroalkenylation of indoles
(Rated as: good idea)

Their examples does not include nitro-alkenes, but all alkenes with any electron-withdrawing group whatsoever worked in their synthesis, so it is highly likely that this can be used to produce 1-(3-indolyl)-2-nitropropenes in a single step from indoles and 3-acetoxy-2-nitro-propene. This can in turn is made by condensing formaldehyde with nitromethane (yielding 2-nitro-propane-1,3-diol), acetylating the diol with Ac₂O or AcCl and distilling in vacuo to give the nitroalkene (se refs at the bottom).

Palladium-catalyzed functionalization of indoles with 2-acetoxymethyl substituted electron-deficient alkenes
Shengming Ma, and Shichao Yu, Tet. Lett. 45(45), 8419-8422 (2004), DOI:10.1016/j.tetlet.2004.08.178

Abstract
A new functionalization of indoles via palladium-catalyzed reaction of indoles and 2-acetoxymethyl substituted electron-deficient alkenes is reported. The reaction was carried out under neutral condition and no isomerization of the carbon–carbon double bond was observed.

Preparation of 3-acetoxy-2-nitro-propene:

Nitromethane + Formaldehyde --1:NaOH--2:Acetylation--> 3-acetoxy-2-nitro-propene
M.B. Frankel, Tetrahedron Suppl. 4, 213-217 (1963)

2-nitro-propane-1,3-diol + acetyl chloride --CH₂Cl₂--> 1,3-diacetoxy-2-nitro-propane --180°C/70-100mmHg--> 3-acetoxy-2-nitro-propene
Klager,K.; Monatsh. Chem. 96, 1-8 (1965)

2-nitro-propane-1,3-diol + acetic acid anhydride -> 1,3-diacetoxy-2-nitro-propane
Carbohydr. Res. 310(3) 191-202 (1998)

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	All 2 posts		Subject: Indole 3-alkylation		Please login to post		Down


		Rhodium (Chief Bee) 09-28-03 00:47 No 461398				Indole 3-alkylation (Rated as: good read)
						For example, 2-dimethylaminoethanal would give DMT, and alpha-bromo-acetaldehyde would give 3-(2-bromoethyl)-indole, which in turn would be ready for alkylation by any dialkylamine to give the corresponding N,N-dialkyltryptamine. A general method for C3 reductive alkylation of indoles Anu Mahadevan,Howard Sarda, Mario Gonzalez, John C. McKew Tetrahedron Letters 44(24), 4589-4591 (2003) (https://www.rhodium.ws/pdf/reductive.3-alkylation.indoles.pdf) DOI:10.1016/S0040-4039(03)01010-4 Abstract General indole C₃ reductive alkylation conditions have been developed. The scope of this reaction includes C₂ unsubstituted indoles, aryl and alkyl aldehydes, as well as N–H and N-alkyl indole substrates.



		Rhodium (Chief Bee) 10-15-04 01:11 No 535894				Pd-catalyzed 3-nitroalkenylation of indoles (Rated as: good idea)
						Their examples does not include nitro-alkenes, but all alkenes with any electron-withdrawing group whatsoever worked in their synthesis, so it is highly likely that this can be used to produce 1-(3-indolyl)-2-nitropropenes in a single step from indoles and 3-acetoxy-2-nitro-propene. This can in turn is made by condensing formaldehyde with nitromethane (yielding 2-nitro-propane-1,3-diol), acetylating the diol with Ac₂O or AcCl and distilling in vacuo to give the nitroalkene (se refs at the bottom). Palladium-catalyzed functionalization of indoles with 2-acetoxymethyl substituted electron-deficient alkenes Shengming Ma, and Shichao Yu, Tet. Lett. 45(45), 8419-8422 (2004), DOI:10.1016/j.tetlet.2004.08.178 Abstract A new functionalization of indoles via palladium-catalyzed reaction of indoles and 2-acetoxymethyl substituted electron-deficient alkenes is reported. The reaction was carried out under neutral condition and no isomerization of the carbon–carbon double bond was observed. Preparation of 3-acetoxy-2-nitro-propene: Nitromethane + Formaldehyde --1:NaOH--2:Acetylation--> 3-acetoxy-2-nitro-propene M.B. Frankel, Tetrahedron Suppl. 4, 213-217 (1963) 2-nitro-propane-1,3-diol + acetyl chloride --CH₂Cl₂--> 1,3-diacetoxy-2-nitro-propane --180°C/70-100mmHg--> 3-acetoxy-2-nitro-propene Klager,K.; Monatsh. Chem. 96, 1-8 (1965) 2-nitro-propane-1,3-diol + acetic acid anhydride -> 1,3-diacetoxy-2-nitro-propane Carbohydr. Res. 310(3) 191-202 (1998) ^{The Hive - Clandestine Chemists Without Borders}

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