A convenient synthesis of tertiary alkyl N-phenylcarbamates from tertiary alcohols and phenyl isocyanate with a lithium alkoxide catalyst

1978 ◽  
Vol 43 (13) ◽  
pp. 2690-2692 ◽  
Author(s):  
William J. Bailey ◽  
James R. Griffith
Keyword(s):  
Phenyl Isocyanate ◽  
Tertiary Alcohols ◽  
Convenient Synthesis ◽  
Tertiary Alkyl

Reactions of Tertiary Hypohalites

1971 ◽  
Vol 49 (16) ◽  
pp. 2664-2671 ◽  
Author(s):  
V. Boido ◽  
O. E. Edwards
Keyword(s):  
Silver Oxide ◽  
Short Chain ◽  
Metallic Silver ◽  
Mercuric Oxide ◽  
Tertiary Alcohols ◽  
Convenient Synthesis ◽  
Homolytic Decomposition ◽  
Tertiary Alkyl

Metallic silver initiates short-chain homolytic decomposition of tertiary alkyl hypochlorites and hypobromites. Evidence is presented that the reaction of tertiary alcohols with silver oxide – mercuric oxide – bromine involves formation and homolytic decomposition of alkyl hypobromite followed by cyclization of γ-bromo alcohols. A convenient synthesis of tricyclo[4.3.1.03,8]decan-4-one (4-proto-adamantanone) is described.

The Thermal Decomposition of Alkoxycarbonyl Thiocyanates and Isothiocyanates

1975 ◽  
Vol 53 (6) ◽  
pp. 907-912 ◽  
Author(s):  
Dennis Liotta ◽  
Robert Engel
Keyword(s):  
Thermal Decomposition ◽  
Primary Alcohols ◽  
Reduced Pressure ◽  
Tertiary Alcohols ◽  
Alkyl Amines ◽  
Tertiary Alkyl

Alkoxycarbonyl thiocyanates and isothiocyanates have been decomposed thermally under reduced pressure at temperatures of 240–375°. Primary systems yield primarily alkyl thiocyanates, whereas secondary and tertiary systems yield alkyl isothiocyanates. The viability of using this reaction in a conversion of primary alcohols to primary alkyl thiols and secondary and tertiary alcohols to tertiary alkyl amines is discussed.

Zn-Mediated Hydrodeoxygenation of Tertiary Alkyl Oxalates

Synlett ◽  
2020 ◽  
Author(s):  
Hegui Gong ◽  
Yang Ye ◽  
Guobin Ma ◽  
Ken Yao
Keyword(s):  
Functional Groups ◽  
Reduction Method ◽  
Structural Motifs ◽  
Tertiary Alcohols ◽  
Tertiary Alkyl

AbstractHerein we describe a general, mild, and scalable method for hydrodeoxygenation of readily accessible tertiary alkyl oxalates by Zn/silane under Ni-catalyzed conditions. The reduction method is suitable for an array of structural motifs derived from tertiary alcohols that bear diverse functional groups, including the synthesis of a key intermediate en route to estrone.

scholarly journals Erratum: Corrigendum: Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines

Nature ◽  
2013 ◽  
Vol 503 (7475) ◽  
pp. 300-300 ◽  
Author(s):  
Sergey V. Pronin ◽  
Christopher A. Reiher ◽  
Ryan A. Shenvi
Keyword(s):  
Tertiary Alcohols ◽  
Tertiary Alkyl

Convenient Synthesis of More Complex 2-Substituted 4(3H)-Quinazolinones via Lithiation of 2-Alkyl-4(3H)-quinazolinones

1999 ◽  
Vol 64 (3) ◽  
pp. 515-526 ◽  
Author(s):  
Keith Smith ◽  
Gamal A. El-Hiti ◽  
Mohamed F. Abdel-Megeed ◽  
Mohamed A. Abdo
Keyword(s):  
Addition Product ◽  
Phenyl Isocyanate ◽  
Lithium Diisopropylamide ◽  
Methyl Group ◽  
Convenient Synthesis

2-Methylquinazolin-4(3H)-one has been doubly lithiated, at nitrogen and in the 2-methyl group, with n-butylithium. The lithium reagent thus obtained reacts with a variety of electrophiles (iodomethane, D2O, phenyl isocyanate, benzaldehyde, benzophenone, cyclopentanone, 2-butanone, carvone) to give the corresponding 2-substituted derivatives in very good yields. Reaction of the dilithio reagent with acetonitrile gives an α,β-unsaturated imine by tautomerization of the initial addition product. Double lithiation of 2-ethyl- and 2-propyl-4(3H)-quinazolinones can be achieved using lithium diisopropylamide and the lithiated reagents thus obtained react with similar electrophiles to give the corresponding products in very good yields. In the reaction of the dianion of the 2-ethyl-4(3H)-quinazolinone with iodine, an oxidatively dimerised product was obtained. Lithiation of 2-unsubstituted 4(3H)-quinazolinone does not take place on C-2 under similar conditions.

Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines

Nature ◽  
2013 ◽  
Vol 501 (7466) ◽  
pp. 195-199 ◽  
Author(s):  
Sergey V. Pronin ◽  
Christopher A. Reiher ◽  
Ryan A. Shenvi
Keyword(s):  
Tertiary Alcohols ◽  
Tertiary Alkyl

The Light-Induced Reaction of Thexyldialkylboranes with Bromine in the Presence of Water. A New and Convenient Synthesis of Tertiary Alcohols Including Those Containing Functional Substituents

Synthesis ◽  
1972 ◽  
Vol 1972 (06) ◽  
pp. 304-306 ◽  
Author(s):  
Herbert C. BROWN ◽  
Yoshinori YAMAMOTO ◽  
Clinton F. LANE
Keyword(s):  
Tertiary Alcohols ◽  
Convenient Synthesis ◽  
Induced Reaction

scholarly journals Tertiary alcohol preferred: Hydroxylation oftrans-3-methyl-L-proline with proline hydroxylases

2011 ◽  
Vol 7 ◽  
pp. 1643-1647 ◽  
Author(s):  
Christian Klein ◽  
Wolfgang Hüttel
Keyword(s):  
Relative Yield ◽  
Heme Iron ◽  
Tertiary Alcohol ◽  
Type Ii ◽  
Tertiary Alcohols ◽  
P450 Monooxygenases ◽  
Non Heme Iron ◽  
Sterically Hindered ◽  
Tertiary Alkyl ◽  
Proline Hydroxylase

The enzymatic synthesis of tertiary alcohols by the stereospecific oxidation of tertiary alkyl centers is a most-straightforward but challenging approach, since these positions are sterically hindered. In contrast to P450-monooxygenases, there is little known about the potential of non-heme iron(II) oxygenases to catalyze such reactions. We have studied the hydroxylation oftrans-3-methyl-L-proline with the α-ketoglutarate (α-KG) dependent oxygenases,cis-3-proline hydroxylase type II andcis-4-proline hydroxylase (cis-P3H_II andcis-P4H). Withcis-P3H_II, the tertiary alcohol product (3R)-3-hydroxy-3-methyl-L-proline was obtained exclusively but in reduced yield (~7%) compared to the native substrate L-proline. Forcis-P4H, a complete shift in regioselectivity from C-4 to C-3 was observed so that the same product as withcis-P3H_II was obtained. Moreover, the yields were at least as good as in control reactions with L-proline (~110% relative yield). This result demonstrates a remarkable potential of non-heme iron(II) oxygenases to oxidize substrates selectively at sterically hindered positions.

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