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Q: Reduction of Ketones in presence of Amines ( No Answer,   6 Comments )
Question  
Subject: Reduction of Ketones in presence of Amines
Category: Science > Chemistry
Asked by: albing-ga
List Price: $15.00
Posted: 13 Jun 2006 14:44 PDT
Expires: 13 Jul 2006 14:44 PDT
Question ID: 737901
I would like to reduce a ketone to a secondary alcohol with an
unprotected amine function in the molecule.  Those should the only
functional groups that would limit my choice of reducing agents. 
Suggestions? Pls suggest approximate conditions also.
Answer  
There is no answer at this time.

Comments  
Subject: Re: Reduction of Ketones in presence of Amines
From: mhitar-ga on 15 Jun 2006 11:50 PDT
 
Amine groups are normally not affected by the reduction agents, do you
have any specific reasons to worry?
Also, you need to tell more details about your system, if you want a
more specific  answer than the recipes from an organic chemistry
textbook, like "try lithium tetrahydridoaluminate in ethoxyethane" or
"sodium borohydride in ethanol".
Subject: Re: Reduction of Ketones in presence of Amines
From: eugene123-ga on 16 Jun 2006 16:14 PDT
 
Can you tell us what the molecule is?
Subject: Re: Reduction of Ketones in presence of Amines
From: albing-ga on 22 Jun 2006 05:55 PDT
 
eugene-123:

Sorry, structure is confidential.  But it is jus alky and aryl stuff.
Subject: Re: Reduction of Ketones in presence of Amines
From: albing-ga on 22 Jun 2006 05:58 PDT
 
mhitar:
Basic organic textbook may work, but I was concerned about the hydride
ions abstracting protons from the amine.  Maybe that's no problem. 
Maybe I just add an extra molar equivalent of hydride? Could you cite
a reference?
Subject: Re: Reduction of Ketones in presence of Amines
From: michalski-ga on 07 Jul 2006 15:47 PDT
 
In 30 ml of heated methanol, dissolve 4.9 mmol of aminoketone and 29.4
mmol of cerium chloride heptahydrate. Cool the mixture to -20C and
while stirring
add 14.7 mmol of sodium borohydride by portions within 20-30 min.
After the mixture is stirred for 1h, slowly warm to room temperature,
stir for 5 h and boil for 2 h. Distill the solvent off, to the residue
add 30 ml of 2 N hydrochloric acid and extract the reaction product
into dichloromethane (2x15 ml). Wash the organic solution with 10 ml
of 20% aqueous ammonia, dry with sodium sulfate, and distill the
solvent off in a vacuum. Subject the residue to chromatography on a
column charged with 10 g of silica gel (eluent benzene). This will
obtain a mixture containing diastereomeric alcohols.

Procedure taken from I. L. Lysenko, A. V. Bekish, and O.G.
Kulinkovich. 2001. Stereoelective Conversion of Ethyl Pipecolinate
into (+)-a- and (+)-b-Conhydrins. Belorussian State University, Minsk.
Subject: Re: Reduction of Ketones in presence of Amines
From: iwannahelp-ga on 07 Jul 2006 18:09 PDT
 
For a system with a ketone and an aniline: 
"LiBEt3H, THF, -78oC"
Pilli, R. A.; Russowsky, D.; Dias, L. C.; J Chem Soc, Perkin Trans 1
[JCPRB4] 1990, 1213.
"Baker's yeast, Saccharose, H2O/EtOH"
Fujisawa, T.; Kishioka, Y.; Hayashi, H.; Chem Lett [CMLTAG] 1987, 129.

For a system with a ketone and an amine:
"NaBH4, EtOH"
Winkler, J. D.; Hershberger, P. M.; J Am Chem Soc [JACSAT] 1989, 111 (13), 4852.
Lamant, M.; Guignard, A.; Helv Chim Acta [HCACAV] 1987, 70, 1279.
"RhCl(COD), MCCPM, NEt3, MeOH"
Takeda, H.; Tachinami, T.; Aburatani, M.; Tetrahedron Lett [TELEAY]
1989, 30 (3), 363.
"Pt, EtOH, H2O"
Tramontini, M.; Synthesis [SYNTBF] 1982 (8), 605.
"1)ZnBr2/MeOH (Zinc bromide and aziridine give a complex which can be
crystallized out) then 2)NaBH4/MeOH"
Bartnik, R.; Lesniak, S.; Laurent, A.; Tetrahedron Lett [TELEAY] 1981, 22, 4811.
"LiAlH(O-tBu)3, THF"
TANDON, V. K.; SINGH, K. A.; AWASTHI, A. K.; KHANNA, J. M.; LAL, B.;
ANAND, N.; Bioorg Med Chem Lett [BMCLE8] 2004, 14 (11), 2867-2870.
"LiBH4, CeCl3, THF"
BARTOLI, G.; BARTOLACCI, M.; CORTESE, M.; MARCANTONI, E.; MASSACCESI,
M.; PELA, R.; SAMBRI, L.; Eur J Org Chem [EJOCFK] 2004, (11),
2359-2366.
"BH3.Py, TiCl4, CH2Cl2"
BARTOLI, G.; BARTOLACCI, M.; CORTESE, M.; MARCANTONI, E.; MASSACCESI,
M.; PELA, R.; SAMBRI, L.; Eur J Org Chem [EJOCFK] 2004, (11),
2359-2366.
"Zn(BH4)2, THF"
ORDONEZ, M.; DE LA CRUZ-CORDERO, R.; QUINONES, C.; GONZALEZ-MORALES,
A.; Chem Commun (Cambridge) [CHCOFS] 2004, (6), 672-673.

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