ChemInform Abstract: Synthetic Methods and Reactions. Part 136. Single-Step One-Carbon Ring Homologation of Cyclic and Polycyclic Hydrocarbons via Their Methyl Alcohols or Carboxylic Acids with Sodium Borohydride/Triflic Acid.

Silylation of ketones, alcohols, mercaptans, and carboxylic acids with N-trimethylsilyl-2-oxazolidinone (TMSO) and triflic acid as catalyst has been described from synthetic and mechanistic points of view.

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ChemInform Abstract: Synthetic Methods and Reactions. Part 134. Preparation of 2-Aryladamantanes and 3-Aryldiamantanes by Improved Ionic Hydrogenation of the Corresponding Tertiary Alcohols with Sodium Borohydride-Triflic Acid or Formic Acid-Triflic Acid.

ChemInform ◽

10.1002/chin.198915133 ◽

1989 ◽

Vol 20 (15) ◽

Author(s):

G. A. OLAH ◽

A. WU ◽

O. FAROOQ

Keyword(s):

Formic Acid ◽

Sodium Borohydride ◽

Ionic Hydrogenation ◽

Synthetic Methods ◽

Triflic Acid ◽

Tertiary Alcohols

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Single-Step Reductive Isomerization of Unsaturated Polycyclics to C4n+6H4n+12 Diamondoid Cage Hydrocarbons with Sodium Borohydride/Triflic Acid

World Scientific Series in 20th Century Chemistry - Across Conventional Lines ◽

10.1142/9789812791405_0174 ◽

2003 ◽

pp. 904-905

Author(s):

George A. Olah ◽

An-hsiang Wu ◽

Omar Farooq ◽

G. K. Surya Prakash

Keyword(s):

Sodium Borohydride ◽

Single Step ◽

Triflic Acid

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Generation of Phosphoranyl Radicals via Photoredox Catalysis Enables Voltage–Independent Activation of Strong C–O Bonds

10.26434/chemrxiv.6349253 ◽

2018 ◽

Author(s):

Erin Stache ◽

Alyssa B. Ertel ◽

Tomislav Rovis ◽

Abigail G. Doyle

Keyword(s):

Carboxylic Acids ◽

Functional Groups ◽

Single Step ◽

Direct Access ◽

Photoredox Catalysis ◽

Acyl Radical ◽

Synthetic Strategy ◽

Acyl Radicals ◽

Benzyl Radicals ◽

Aliphatic Carboxylic Acids

Alcohols and carboxylic acids are ubiquitous functional groups found in organic molecules that could serve as radical precursors, but C–O bonds remain difficult to activate. We report a synthetic strategy for direct access to both alkyl and acyl radicals from these ubiquitous functional groups via photoredox catalysis. This method exploits the unique reactivity of phosphoranyl radicals, generated from a polar/SET crossover between a phosphine radical cation and an oxygen centered nucleophile. We first show the desired reactivity in the reduction of benzylic alcohols to the corresponding benzyl radicals with terminal H-atom trapping to afford the deoxygenated product. Using the same method, we demonstrate access to synthetically versatile acyl radicals which enables the reduction of aromatic and aliphatic carboxylic acids to the corresponding aldehydes with exceptional chemoselectivity. This protocol also transforms carboxylic acids to heterocycles and cyclic ketones via intramolecular acyl radical cyclizations to forge new C–O, C–N and C–C bonds in a single step.

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