Stereoselective Hydroxyallylation of Cyclopropenes with Cyclopropanols via NHC Catalysis of Transient Organozinc Species DOI Creative Commons

Kento Tsukiji,

Arimasa Matsumoto, Kazuya Kanemoto

et al.

Published: Dec. 20, 2023

A stereoselective hydroxyallylation reaction of cyclopropenes with cyclopropanols is achieved under zinc-mediated conditions, affording densely functionalized cyclopropanes excellent diastereocontrol over three contiguous stereocenters within and outside the cyclopropane ring. racemic variant synergistically promoted by catalytic N-heterocyclic carbene (NHC) organic base (DBU), whereas chiral amino alcohol-derived bifunctional NHC enables a enantioselective variant. Mechanistically, features transient generation enolized zinc homoenolate via ring-opening cyclopropoxide enolization resulting homoenolate, followed its addition to cyclopropene as prochiral allylzinc nucleophile.

Language: Английский

Ring‐Opening Cross‐Coupling/Cyclization Reaction of Cyclopropanols with Organic Compounds DOI
Fatemeh Doraghi,

Seyedeh Pegah Aledavoud,

Azadeh Fakhrioliaei

et al.

ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(32)

Published: Aug. 23, 2023

Abstract Cyclopropanols, due to their particular chemistry, can participate in various synthetic reactions with retention or cleavage of the strained three‐membered ring. Direct cross‐coupling ring‐opening reaction such molecules access organic compounds, as ketones has great importance medicinal chemistry and material sciences. Hence, coupling reaction/cyclization cyclopropanols for constructing new valuable presence a transition metal catalyst under metal‐free conditions is described this context. The features are discussed, mechanisms challenging highlighted.

Language: Английский

Citations

12
Synthesis of Vicinal anti-Amino Alcohols from N-tert-Butanesulfinyl Aldimines and Cyclopropanols DOI Creative Commons
Sandra Hernández-Ibáñez,

Juan F. Ortuño,

Ana Sirvent

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(9), P. 6193 - 6204

Published: April 13, 2024

The stereoselective synthesis of vicinal amino alcohols derivatives from 1-substituted cyclopropanols and chiral

Language: Английский

Citations

1
Stereoselective Hydroxyallylation of Cyclopropenes with Cyclopropanols via NHC Catalysis of Transient Organozinc Species DOI Creative Commons

Kento Tsukiji,

Arimasa Matsumoto, Kazuya Kanemoto

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 7, 2024

A stereoselective hydroxyallylation reaction of cyclopropenes with cyclopropanols is achieved under zinc-mediated conditions, affording densely functionalized cyclopropanes excellent diastereocontrol over three contiguous stereocenters within and outside the cyclopropane ring. racemic variant synergistically promoted by catalytic N-heterocyclic carbene (NHC) organic base, whereas chiral amino alcohol-derived bifunctional NHC enables a enantioselective variant. The likely involves generation enolized zinc homoenolate via ring-opening cyclopropoxide enolization resulting homoenolate, followed its addition to cyclopropene as prochiral allylzinc nucleophile. Our mechanistic investigations highlighted transient nature which, once generated from thermodynamically predominant cyclopropoxide, immediately proceeds allylzincation cyclopropene. not only promotes rate-determining but also engages in process. cyclopropylzinc species undergoes partial situ protonation while partially remaining intact, thereby leaving an opportunity for trapping external electrophile.

Language: Английский

Citations

1
Stereoselective Hydroxyallylation of Cyclopropenes with Cyclopropanols via NHC Catalysis of Transient Organozinc Species DOI Creative Commons

Kento Tsukiji,

Arimasa Matsumoto, Kazuya Kanemoto

et al.

Published: Dec. 27, 2023

A stereoselective hydroxyallylation reaction of cyclopropenes with cyclopropanols is achieved under zinc-mediated conditions, affording densely functionalized cyclopropanes excellent diastereocontrol over three contiguous stereocenters within and outside the cyclopropane ring. racemic variant synergistically promoted by catalytic N-heterocyclic carbene (NHC) organic base (DBU), whereas chiral amino alcohol-derived bifunctional NHC enables a enantioselective variant. Mechanistically, features transient generation enolized zinc homoenolate via ring-opening cyclopropoxide enolization resulting homoenolate, followed its addition to cyclopropene as prochiral allylzinc nucleophile.

Language: Английский

Citations

1
Stereoselective Hydroxyallylation of Cyclopropenes with Cyclopropanols via NHC Catalysis of Transient Organozinc Species DOI Creative Commons

Kento Tsukiji,

Arimasa Matsumoto, Kazuya Kanemoto

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(46)

Published: Aug. 7, 2024

Abstract A stereoselective hydroxyallylation reaction of cyclopropenes with cyclopropanols is achieved under zinc‐mediated conditions, affording densely functionalized cyclopropanes excellent diastereocontrol over three contiguous stereocenters within and outside the cyclopropane ring. racemic variant synergistically promoted by catalytic N‐heterocyclic carbene (NHC) organic base, whereas chiral amino alcohol‐derived bifunctional NHC enables a enantioselective variant. The likely involves generation enolized zinc homoenolate via ring‐opening cyclopropoxide enolization resulting homoenolate, followed its addition to cyclopropene as prochiral allylzinc nucleophile. Our mechanistic investigations highlighted transient nature which, once generated from thermodynamically predominant cyclopropoxide, immediately proceeds allylzincation cyclopropene. not only promotes rate‐determining but also engages in process. cyclopropylzinc species undergoes partial situ protonation while partially remaining intact, thereby leaving an opportunity for trapping external electrophile.

Language: Английский

Citations

0
Six-membered ring systems: With O and/or S atoms DOI
Clementina M.M. Santos, Artur M. S. Silva

Progress in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 421 - 484

Published: Jan. 1, 2024

Language: Английский

Citations

0
Stereoselective Hydroxyallylation of Cyclopropenes with Cyclopropanols via NHC Catalysis of Transient Organozinc Species DOI Creative Commons

Kento Tsukiji,

Arimasa Matsumoto, Kazuya Kanemoto

et al.

Published: Dec. 20, 2023

A stereoselective hydroxyallylation reaction of cyclopropenes with cyclopropanols is achieved under zinc-mediated conditions, affording densely functionalized cyclopropanes excellent diastereocontrol over three contiguous stereocenters within and outside the cyclopropane ring. racemic variant synergistically promoted by catalytic N-heterocyclic carbene (NHC) organic base (DBU), whereas chiral amino alcohol-derived bifunctional NHC enables a enantioselective variant. Mechanistically, features transient generation enolized zinc homoenolate via ring-opening cyclopropoxide enolization resulting homoenolate, followed its addition to cyclopropene as prochiral allylzinc nucleophile.

Language: Английский

Citations

0