Structure-guided insights into non-catalytic (α-hydroxy)alkylation of olefins with alcohols

New "olefin-alcohol" pairs were involved in the non-catalytic (α-hydroxy)alkylation process at 350 °C - the addition reaction of MeOH, EtOH or 2-PrOH to styrene, cyclohexene, 1-heptene, and limonene to produce carbon-chain elongated alcohols. The contribution of different side reactions (t...

Full description

Saved in:
Bibliographic Details
Published in:New journal of chemistry 2022-05, Vol.46 (2), p.9775-9784
Main Author: Chibiryaev, Andrey M
Format: Article
Language:English
Subjects:
Alcohol
Alkenes
Alkylation
Butanol
Cascade chemical reactions
Dehydration
Selectivity
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:New "olefin-alcohol" pairs were involved in the non-catalytic (α-hydroxy)alkylation process at 350 °C - the addition reaction of MeOH, EtOH or 2-PrOH to styrene, cyclohexene, 1-heptene, and limonene to produce carbon-chain elongated alcohols. The contribution of different side reactions (transfer hydrogenation, alcohol dehydration, C -alkoxylation, etc. ) was described for the first time, and the chemo- and regio-selectivity was evaluated for each pair. As proof-of-concept, the ability of an olefinic precursor to participate in a two-step elimination-(α-hydroxy)alkylation tandem reaction with alcohols was confirmed: isobutylene generated in situ from tert -butanol at 350 °C reacted with MeOH to give two isomeric alcohols (isoamyl and neopentyl alcohols) with 34% selectivity. New experimental data on the mutual reactivity of alcohols and olefins were obtained at 350 °C and a surrogate for olefins was suggested in return.
ISSN:1144-0546
1369-9261
DOI:10.1039/d2nj00155a