Lithium Tris[ (3-tert-butyl-3-pentyl)oxy] Aluminum Hydride: A Selective Reagent for Reduction of Cyclic, Bicyclic and Open-Chain Cram Type Ketones

Synlett ◽  
1993 ◽  
Vol 1993 (08) ◽  
pp. 585-587 ◽  
Author(s):  
G. Boireau ◽  
A. Deberly ◽  
R. Toneva
Keyword(s):  
Aluminum Hydride ◽  
Open Chain ◽  
Tert Butyl ◽  
Selective Reagent

THE SYNTHESIS OF SOME INDOLYLALKYLAMINOALCOHOLS

1960 ◽  
Vol 38 (9) ◽  
pp. 1434-1438 ◽  
Author(s):  
Gerassimos Frangatos ◽  
Geza Kohan ◽  
Francis L. Chubb
Keyword(s):  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Reductive Cleavage ◽  
Lithium Aluminum ◽  
Carbonyl Groups ◽  
Open Chain ◽  
Hydride Reduction

A series of 3-indolylalkylaminoalcohols have been obtained from the lithium aluminum hydride reduction of the amides prepared by the reaction of 3-indoleglyoxylyl chloride and 2-methyl-3-indoleglyoxylyl chloride with primary aminoalcohols. When acetone was used as solvent in the reaction of 3-indoleglyoxylyis chloride and either 2-aminoethanol or 3-aminopropanol, the solvent participated in the reaction resulting in the formation of 2,2-dimethyl-3-(3-indoleglyoxyl)oxazolidine and 2,2-dimethyl-3-(3-indoleglyoxyl)tetrahydro-1,3-oxazine respectively. When the latter two compounds were reduced by lithium aluminum hydride, both carbonyl groups were completely reduced and reductive cleavage of the oxazolidine and tetrahydro-1,3-oxazine rings occurred to form the corresponding open-chain alcohols.

Record-Breaking Steric Crowding in Trialkylamines Prepared by Oxidative Ring Opening

Synthesis ◽  
2020 ◽  
Vol 52 (24) ◽  
pp. 3801-3810
Author(s):  
Klaus Banert ◽  
Manuel Heck ◽  
Andreas Ihle ◽  
Erik Michael ◽  
Richard Weber
Keyword(s):  
Ring Opening ◽  
Room Temperature ◽  
Osmium Tetroxide ◽  
Model Compound ◽  
Ring Cleavage ◽  
Open Chain ◽  
Tert Butyl ◽  
Steric Crowding ◽  
Acid Catalyzed ◽  
Subsequent Acid

AbstractEpoxidation of olefinic heterocyclic amines and subsequent acid-catalyzed hydrolysis or alternatively the direct dihydroxylation with the help of osmium tetroxide led to diols, which underwent ring cleavage in the presence of lead tetraacetate to give 3-isopropyl-2,2,4,4-tetramethyl-3-azahexanedial and 3-tert-butyl-2,2,4,4-tetramethyl-3-azapentanedial. Whereas the former dialdehyde is a highly unstable model compound because of a rapid intramolecular aldol reaction, the latter product proves to be isolable at room temperature. Furthermore, this compound is the first open-chain tri-tert-alkylamine establishing in a new record of steric crowding in tertiary amines. Strong tendencies to a Hofmann-like elimination reaction or to ring-closing reactions were observed when the aldehyde units of 3-tert-butyl-2,2,4,4-tetramethyl-3-azapentanedial were transformed into other functionalities, since both types of reactions led to a significantly decrease of the steric stress.

Reactions of Acenaphthenediimine Aluminum Hydride with 1,3-Dicyclohexylcarbodiimide and 2,6-Di-tert-Butyl-4-Methylphenol

2019 ◽  
Vol 45 (9) ◽  
pp. 637-643 ◽  
Author(s):  
V. G. Sokolov ◽  
T. S. Koptseva ◽  
M. V. Moskalev ◽  
E. V. Baranov ◽  
I. L. Fedyushkin
Keyword(s):  
Aluminum Hydride ◽  
Tert Butyl

Structural studies of organoboron compounds. LV. N,N′-Di-tert-butyl-N,N′- dihydroxypropane-1,3-diamine(O-B)ethoxydiphenylborane and N1,N2-di-tert-butyl-N1,N2-dihydroxy-1-phenylpropane-1,3-diamine(N2-O-B)hydroxydiphenylborane

1992 ◽  
Vol 70 (7) ◽  
pp. 2033-2039 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Gottfried Lubkowitz ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Hydrogen Bonds ◽  
Least Squares ◽  
Direct Methods ◽  
Structural Studies ◽  
Open Chain ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Bond Lengths ◽  
Tert Butyl ◽  
Intramolecular Hydrogen

The 1,3-propanediamine derivatives N,N′-di-tert-butyl-N,N′-dihydroxy-1,3-propanediamine and N,N′-di-tert-butyl-N,N′-dihydroxy-1-phenyl-1,3-propanediamine have been prepared and reacted with oxybis(diphenylborane) to yield, respectively, the crystalline organoboron compounds N,N′-di-tert-butyl-N,N′-dihydroxypropane-1,3-diamine(O-B)-ethoxydiphenylborane, 5a, and N1,N2-di-tert-butyl-N1,N2-dihydroxy-1-phenylpropane-1,3-diamine(N2-O-B)-hydroxydiphenylborane, 5b. Crystals of 5a are monoclinic, C2/c, a = 35.402(1), b = 9.212(2), c = 18.101(2) Å, β = 116.688(3)°, Z = 8, ρc = 1.079 g cm−3, and crystals of 5b are monoclinic, P21/c, a = 12.899(4), b = 12.571(4), c = 17.412(3) Å, β = 90.02(2)°, Z = 4, ρc = 1.121 g cm−3. The structures were solved by direct methods and were refined by full-matrix least-squares procedures to final R values of 0.047 and 0.041 for 2492 and 3334 reflections with I ≥ 3σ(I), respectively. Compounds 5a and 5b are open-chain hydroxylamine adducts of diphenylborinic acid and ethyl diphenylborinate, respectively. Both of these compounds are stabilized by a system of three intramolecular hydrogen bonds [Formula: see text]. Bond lengths involving the tetrahedrally coordinated boron atoms are: (C)O—B = 1.457(3), (N)O—B = 1.558(3), and C—B = 1.613(4) and 1.615(4) Å for 5a; (H)O—B = 1.475(3), (N)O—B = 1.562(2), and C—B = 1.618(3) and 1.619(3) Å for 5b.

Synthesis of cedranoid sesquiterpenes. V. The biotols

1988 ◽  
Vol 66 (11) ◽  
pp. 2805-2815 ◽  
Author(s):  
Peter Yates ◽  
Rupinder S. Grewal ◽  
Peter C. Hayes ◽  
Jeffery F. Sawyer
Keyword(s):  
Hydrogen Chloride ◽  
Hydrogen Fluoride ◽  
Sodium Borohydride ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Butyl Alcohol ◽  
Lithium Aluminum ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Cerium Trichloride

Reduction of dimethyl 3-hydroxy-4,4,8-trimethyl-6-oxo-cis-bicyclo[3.3.0]octa-2,7-diene-1,2-dicarboxylate (8) with lithium and ammonia gives dimethyl 3-hydroxy-4,4,exo-8-trimethyl-6-oxo-cis-bicyclo[3.3.0]oct-2-ene-1,2-dicarboxylate (9), which on acetylation, reduction with sodium borohydride, and methanolysis gives dimethyl 3,exo-6-dihydroxy-4,4,exo-8-trimethyl-cis-bicyclo[3.3.0]oct-2-ene-1,2-dicarboxylate (12). This on 2-decarbomethoxylation followed by treatment with lithium acetylide in the presence of cerium trichloride gives methyl 3-ethynyl-3,exo-6-dihydroxy-4,4,exo-8-trimethyl-cis-bicyclo[3.3.0]octane-1-carboxylate (21), which on hydration, diacetylation, and treatment with tri-n-butyltin hydride and azoisobutyronitrile is converted to methyl exo-6-acetoxy-3-acetyl-4,4,exo-8-trimethyl-cis-bicyclo[3.3.0]octane-1-carboxylate (31). Methanolysis of 31. tert-butyldimethylsilylation, and reaction with potassium tert-butoxide in tert-butyl alcohol gives exo-4-tert-butyldimethylsilyloxy-exo-2,6,6-trimethyl[5.3.11,5]undecane-8,10-dione (35). This on treatment with lithium aluminum hydride followed by oxidation and hydrogenation provides the corresponding 10-deoxo compound, 39. Reaction of this with methyllithium, dehydration, and desilylation with hydrogen fluoride in acetonitrile gives a mixture of (±)-α-biotol (1) and (±)-β-biotol (2); desilylation with hydrogen chloride in methanol gives solely (±)-1.

A 2-Azapentadienyl Carbanion: a Nonstereospecific Electrocyclization

1975 ◽  
Vol 53 (3) ◽  
pp. 355-365 ◽  
Author(s):  
D. H. Hunter ◽  
R. P. Steiner
Keyword(s):  
Proton Transfer ◽  
Transfer Reaction ◽  
Proton Transfer Reaction ◽  
Butyl Alcohol ◽  
Open Chain ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Cis And Trans ◽  
Protic Media

Treatment of 1,3,5-triphenyl-4-aza-1,3-pentadiene under selected basic conditions leads to either isomerization among the azapentadienes or to cyclization. Analysis of the products from reaction under aprotic conditions (LiTMP in THF) suggested that the open-chain delocalized carbanion exists in both the W and sickle forms. The open-chain anions were observed to electrocyclize in a nonstereospecific manner to produce a 1:1 mixture of cis- and trans-2,4,5-triphenyl-1-pyrrolines. Reaction in protic media (methanol and tert-butyl alcohol) produced a 1,5-proton transfer as well as cyclization. The details of the 1,5-proton transfer reaction were elucidated using methanol-O-d and the collapse preferences and intramolecularity in this medium were determined.

scholarly journals Nucleophilic transformations of azido-containing carbonyl compounds via protection of azido group

2021 ◽  
Author(s):  
Takahiro Aimi ◽  
Tomohiro Meguro ◽  
Akihiro Kobayashi ◽  
Takamitsu Hosoya ◽  
Suguru Yoshida
Keyword(s):  
Carbonyl Compounds ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Azido Group ◽  
Carbonyl Groups ◽  
Tert Butyl

Nucleophilic transformations of azido-containing carbonyl compounds are disclosed. The phosphazide formation from azides and di(tert-butyl)(4-(dimethylamino)phenyl)phosphine (Amphos) enabled transformations of carbonyl groups with nucleophiles such as lithium aluminum hydride and organometallic...

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