Organocatalytic Asymmetric Allylic Benzylborylation via Fluoride-Assisted Catalytic Generation of α-Boryl Carbanionic Intermediates DOI Creative Commons
Jordi Duran, Paula Rodríguez,

W.A.H. Vermeer

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 20, 2024

Herein we describe the organocatalytic asymmetric allylic benzylborylation of allyl fluorides with α-silyl benzylboronic esters. The catalytic protocol leverages singular features fluoride as an unconventional leaving group, enabling generation reactive α-boryl carbanion species through desilylative activation. It allows construction a wide set homoallylic benzylated organoboronates bearing two contiguous stereocenters. chiral boronate installed in products serves synthetic lynchpin to construct complex chemical architectures stereospecific manner.

Язык: Английский

L/Z-ligand type amphoterism of an acridinium unit DOI Creative Commons
Elishua D. Litle,

Shantabh Bedajna,

François P. Gabbaı̈

и другие.

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

As part of our study ambiphilic carbenium-based ligands, we now report on the coordination chemistry known acridinium phosphine ligand [(o-Ph2P(C6H4)Acr)]+ ([Lacr]+, Acr = 9-N-methylacridinium) towards rhodium(i) reagents. While simple complex [LacrRh(COD)Cl]+ ([1]+) is obtained from [Lacr]+ and [Rh(COD)Cl]2 (COD 1,5-cyclooctadiene) in CH2Cl2, use [Rh(COE)2Cl]2 (COE cyclooctene) MeCN affords [(o-Ph2P(C6H4)Acr)Rh(MeCN)2Cl]2 2+ ([2]2 2+), a chloride-bridged dimeric which each rhodium atom involved Rh→Ccarb dative bond (Ccarb C9 atom), indicating Z-type behavior unit. The same reaction CH2Cl2 [(o-Ph2P(C6H4)Acr)RhCl]2 ([3]2 square planar assumes role an η2-heteroarene, L-type ligand. All complexes, have been structurally characterized as their triflate salts, can be interconverted into one another via exchange or displacement reactions. These experimental results, supported by computational analyses, show that unit displays ligand-type amphoterism it easily reversibly switches to response changes sphere metal center.

Язык: Английский

Процитировано

0
Boron‐Nitrogen‐Containing Benzene Valence Isomers DOI Creative Commons

Tomoya Ozaki,

Shih‐Yuan Liu

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Июль 26, 2024

Abstract Benzene is one of the most ubiquitous structural motifs in chemistry. The valence isomers benzene have also attracted synthetic chemists’ attention due to their unique structures, bonding, and reactivity. We been investigating boron‐nitrogen‐containing via photoisomerization 1,2‐azaborines. In this contribution, we summarize recent developments these highly strained BN‐heterocyclic compounds including synthesis, characterization, proposed mechanism formation, potential applications.

Язык: Английский

Процитировано

3
Organocatalytic Asymmetric Allylic Benzylborylation via Fluoride-Assisted Catalytic Generation of α-Boryl Carbanionic Intermediates DOI Creative Commons
Jordi Duran, Paula Rodríguez,

W.A.H. Vermeer

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 20, 2024

Herein we describe the organocatalytic asymmetric allylic benzylborylation of allyl fluorides with α-silyl benzylboronic esters. The catalytic protocol leverages singular features fluoride as an unconventional leaving group, enabling generation reactive α-boryl carbanion species through desilylative activation. It allows construction a wide set homoallylic benzylated organoboronates bearing two contiguous stereocenters. chiral boronate installed in products serves synthetic lynchpin to construct complex chemical architectures stereospecific manner.

Язык: Английский

Процитировано

0