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1.
Org Lett ; 26(15): 3258-3262, 2024 Apr 19.
Article in English | MEDLINE | ID: mdl-38568149

ABSTRACT

An efficient cobalt-catalyzed selective hydroboration of 1,3-enynes with HBpin toward 1,3-dienylboronate esters is disclosed. With a commercially available catalytic system of Co(acac)2 and dppf, the hydroboration reactions proceeded well to afford a wide range of 1,3-dienylborates in moderate to high yields. This protocol features a cheap base-metal catalytic system, broad substrate scope, excellent selectivity, easy gram-scale preparation, and good functional group tolerance and provides access to synthetically valuable 1,3-dienylborates.

2.
Angew Chem Int Ed Engl ; 62(49): e202314006, 2023 Dec 04.
Article in English | MEDLINE | ID: mdl-37847644

ABSTRACT

Mixed-valence (MV) dimers have been extensively investigated, however, the structure and properties of purely organic MV trimers based on open-shell polycyclic aromatic hydrocarbons remain elusive. Herein, unprecedented MV BN-doped corannulene radical cations [BN-Cor1]3 ⋅⋅2+ ⋅ 2[BArylF 4 ]- and [BN-Cor2]3 ⋅⋅2+ ⋅ 2[BArylF 4 ]- were synthesized via chemical oxidation, and their structures were unambiguously confirmed by single-crystal X-ray diffraction. These uncommon radical cations consist of three corannulene cores and two [BArylF 4 ]- anions, and three corannulene motifs [BN-Cor1]3 ⋅⋅2+ and [BN-Cor2]3 ⋅⋅2+ in the unit cell exhibit a trimer structure with a slipped π-stacking configuration. Detailed structural analyses further revealed that the corannulene cores exhibit an infinite layered self-assembly configuration, allowing their potential applications as building blocks for molecular conductors. The detection of a forbidden transition (Δms =±2) by electron paramagnetic resonance (EPR) spectroscopy further confirmed the existence of two unpaired electrons in the π-trimers and the MV characteristic of these two species. Variable-temperature EPR and conductivity measurements suggested that the BN-doped π-trimers exhibited antiferromagnetic coupling and conductivity properties.

3.
Angew Chem Int Ed Engl ; 62(31): e202306248, 2023 Aug 01.
Article in English | MEDLINE | ID: mdl-37265364

ABSTRACT

Enantioselective functionalization of racemic alkyl halides is an efficient strategy to assemble complex chiral molecules, but remains one of the biggest challenges in organic chemistry. The distant and selective activation of unreactive C-H bonds in alkyl halides has received growing interest as it enables rapid generation of molecular complexity from simple building blocks. Here, we reported a cobalt-catalyzed remote borylation of alkyl (pseudo)halides (alkyl-X, X=I, Br, Cl, OTs) with pinacolborane (HBpin) and presented a robust approach for the generation of valuable chiral secondary organoboronates from racemic alkyl halides. This migration borylation reaction is compatible with primary, secondary, and tertiary bromides, offering direct access to a broad range of alkylboronates. The extension of this catalytic system to the borylation of aryl halides was also demonstrated. Preliminary mechanistic studies revealed that this remote borylation involved a radical reaction pathway.

4.
J Org Chem ; 88(11): 7525-7534, 2023 Jun 02.
Article in English | MEDLINE | ID: mdl-37196236

ABSTRACT

We describe a general and efficient transition-metal free C-C bond cross-coupling of (hetero)aryl ethers and diarylmethanes via C(sp2)-O bond cleavage. The coupling reactions mediated by KHMDS proceeded well with high efficiency, broad substrate scope, and good functional group tolerance. The robustness and practicability of this protocol also have been demonstrated by easy gram-scale preparation and diversified product derivatization.

5.
Org Biomol Chem ; 21(20): 4304-4308, 2023 May 24.
Article in English | MEDLINE | ID: mdl-37161518

ABSTRACT

An efficient catalyst-free C(sp3)-H bond functionalization of methyl azaarenes with heteroaromatic trifluoromethyl ketone hydrates in neat water has been developed for the synthesis of α-trifluoromethyl tertiary alcohols bearing N-heteroaromatics. This method not only features excellent efficiency, broad substrate scope, catalyst-free conditions, and easy gram-scale preparation but also represents a new and rare example of "all-water" synthesis of trifluoromethylated molecules.

6.
Angew Chem Int Ed Engl ; 62(5): e202215455, 2023 Jan 26.
Article in English | MEDLINE | ID: mdl-36445794

ABSTRACT

Remote functionalization involving a fascinating chain-walking process has emerged as a powerful strategy for the rapid access to value-added functional molecules from readily available feedstocks. However, the scope of current methods is predominantly limited to mono- and di-substituted alkenes. The remote functionalization of multi- and heteroatom-substituted alkenes is challenging, and the use of alkynes in the chain walking is unexplored. We herein report a rhodium catalyzed remote borylation of internal alkynes, offering an unprecedented reaction mode of alkynes for the preparation of synthetically valuable 1,n-diboronates. The regioselective distal migratory hydroboration of sterically hindered tri- and tetra-substituted vinylboronates is also demonstrated to furnish various multi-boronic esters. Synthetic utilities are highlighted through the selective manipulation of the two boryl groups in products such as the regioselective cross coupling, oxidation, and amination.

7.
Angew Chem Int Ed Engl ; 61(41): e202209004, 2022 10 10.
Article in English | MEDLINE | ID: mdl-35997133

ABSTRACT

Oxidation of C-B bonds is extensively used in organic synthesis, materials science, and chemically biology. However, these oxidations are usually limited to the oxidation of C(sp3 )-B and C(sp2 )-B bonds. The C(sp)-B bond oxidation is rarely developed. Herein we present a novel strategy for the preparation of γ-lactones via the oxidation of enynyl boronates. This process successively involves the C(sp)-B bond oxidation, the epoxidation of C-C double bond and the lactonization. This protocol provided various γ-lactones and unsaturated butenolides efficiently that are prevalent in numerous nature products and bioactive molecules. Most importantly, asymmetric oxidative lactonization of enynyl boronates was also achieved, providing chiral γ-lactones in high enantioselectivities and diastereoselectivities. The versatile transformations and ubiquity of γ-lactones shed light on the importance of this strategy in the construction and late-stage functionalization of complex molecules.


Subject(s)
Lactones , Oxidative Stress , Chemistry Techniques, Synthetic , Lactones/chemistry , Oxidation-Reduction
8.
Angew Chem Int Ed Engl ; 61(29): e202117413, 2022 07 18.
Article in English | MEDLINE | ID: mdl-35488385

ABSTRACT

Catalytic asymmetric hydroboration of alkenes is a powerful tool for the synthesis of natural products, agrochemicals, and pharmaceuticals via the versatile transformations of chiral alkyl boronic esters. However, the scope of available alkenes is limited to styrenes, activated alkenes, and compounds with directing groups. The catalytic enantioselective hydroboration of heteroatom-substituted alkenes is rarely explored and those catalyzed by earth-abundant metals are yet to be reported. Herein, we report a cobalt-catalyzed asymmetric hydroboration of ketone-derived silyl enol ethers and provide a convenient approach to access valuable enantiopure ß-hydroxy boronic esters. This protocol features mild reaction conditions, a broad substrate scope, and excellent enantioselectivities (up to 99 % ee). This approach was applied in the successful synthesis of salmeterol and albuterol, demonstrating its potential to streamline complex molecule synthesis.


Subject(s)
Ethers , Ketones , Alcohols , Alkenes/chemistry , Catalysis , Cobalt , Esters , Ethers/chemistry , Ketones/chemistry , Stereoisomerism
9.
J Org Chem ; 87(10): 6951-6959, 2022 05 20.
Article in English | MEDLINE | ID: mdl-35486740

ABSTRACT

An efficient palladium-catalyzed Suzuki-Miyaura cross-coupling reaction of oxygen atom-substituted allylboronates with aryl/vinyl bromides, iodides, and triflates has been developed. The present coupling reactions proceeded smoothly to provide a variety of allylic siloxanes with high efficiency and excellent regioselectivity. This protocol features broad substrate scope, excellent functional group tolerance, and easy gram-scale preparation, and offers an alternative approach for the synthesis of allylic alcohols and their derivatives.


Subject(s)
Oxygen , Palladium , Catalysis
10.
Chemistry ; 28(15): e202103851, 2022 Mar 10.
Article in English | MEDLINE | ID: mdl-34967479

ABSTRACT

We present herein a novel strategy for the preparation of ketones from aldehydes and allylic boronic esters. This reaction involves the allylation of aldehydes with allylic boronic esters and the Rh-catalyzed chain-walking of homoallylic alcohols. The key to this successful development is the protodeboronation of alkenyl borylether intermediate via a tetravalent borate anion species in the presence of KHF2 and MeOH. This approach features mild reaction conditions, broad substrate scope, and excellent functional group tolerance. Mechanistic studies also supported that the tandem allylation and chain-walking process were involved.


Subject(s)
Aldehydes , Rhodium , Catalysis , Ketones , Stereoisomerism
11.
Chem Commun (Camb) ; 58(2): 302-305, 2021 Dec 23.
Article in English | MEDLINE | ID: mdl-34889327

ABSTRACT

The Co-catalyzed remote hydroboration and alkene isomerization of allylic siloxanes were realized by a ligand-controlled strategy. The remote hydroboration with dcype provided borylethers, while xantphos favored the formation of silyl enol ethers.

12.
Org Lett ; 23(24): 9580-9585, 2021 Dec 17.
Article in English | MEDLINE | ID: mdl-34860021

ABSTRACT

An efficient rhodium-catalyzed ß-dehydroborylation of aldehyde-derived silyl enol ethers (SEEs) with bis(pinacolato)diboron (B2pin2) is disclosed. The borylation reactions proceeded well with alkyl- and aryl-substituted SEEs, affording a wide array of valuable functionalized ß-boryl silyl enolates with high efficiency and excellent stereoselectivity. Moreover, the borylated products, through versatile carbon-boron bond transformations, were readily converted into diverse synthetically useful molecules, including α-hydroxy ketones, functionalized SEEs, and gem-difunctionalized aldehydes.

13.
Org Lett ; 23(22): 8766-8771, 2021 Nov 19.
Article in English | MEDLINE | ID: mdl-34738819

ABSTRACT

We describe a general and efficient protocol for the synthesis of organophosphine compounds from phenols and phosphines (R2PH) via a metal-free C-O bond cleavage and C-P bond formation process. This approach exhibits broad substrate scope and excellent functional group tolerance. The synthetic utilities of this protocol were demonstrated by the synthesis of chiral ligands via the various transformations of cyano groups and their applications in asymmetric catalysis.

14.
Org Lett ; 23(20): 7797-7802, 2021 10 15.
Article in English | MEDLINE | ID: mdl-34581587

ABSTRACT

We here present a generally applicable cobalt-catalyzed remote hydroboration of alkenyl amines, providing a practical strategy for the preparation of borylamines and aminoalcohols. This method shows broad substrate scope and good functional group tolerance, tolerating a series of alkenyl amines, including alkyl-alkyl amines, alkyl-aryl amines, aryl-aryl amines, and amides. Of note, this protocol is also compatible with a variety of natural products and drug derivatives. Preliminary mechanistic studies suggest that this transformation involves an iterative chain walking and hydroboration sequence.

15.
Org Biomol Chem ; 19(35): 7633-7640, 2021 09 15.
Article in English | MEDLINE | ID: mdl-34524311

ABSTRACT

A general method for the demethylation, debenzylation, and deallylation of aryl ethers using HPPh2 and tBuOK is reported. The reaction features mild and metal-free reaction conditions, broad substrate scope, good functional group compatibility, and high chemical selectivity towards aryl ethers over aliphatic structures. Notably, this approach is competent to selectively deprotect the allyl or benzyl group, making it a general and practical method in organic synthesis.

16.
J Am Chem Soc ; 143(29): 10902-10909, 2021 07 28.
Article in English | MEDLINE | ID: mdl-34254797

ABSTRACT

The asymmetric hydroboration of alkenes has proven to be among the most powerful methods for the synthesis of chiral boron compounds. This protocol is well suitable for activated alkenes such as vinylarenes and alkenes bearing directing groups. However, the catalytic enantioselective hydroboration of O-substituted alkenes has remained unprecedented. Here we report a Rh-catalyzed enantioselective hydroboration of silyl enol ethers (SEEs) that utilizes two new chiral phosphine ligands we developed. This approach features mild reaction conditions and a broad substrate scope as well as excellent functional group tolerance, and enables highly efficient preparation of synthetically valuable chiral borylethers.

17.
J Am Chem Soc ; 142(42): 18118-18127, 2020 Oct 21.
Article in English | MEDLINE | ID: mdl-32981320

ABSTRACT

The rhodium-catalyzed deoxygenation and borylation of ketones with B2pin2 have been developed, leading to efficient formation of alkenes, vinylboronates, and vinyldiboronates. These reactions feature mild reaction conditions, a broad substrate scope, and excellent functional-group compatibility. Mechanistic studies support that the ketones initially undergo a Rh-catalyzed deoxygenation to give alkenes via boron enolate intermediates, and the subsequent Rh-catalyzed dehydrogenative borylation of alkenes leads to the formation of vinylboronates and diboration products, which is also supported by density functional theory calculations.

18.
ACS Appl Mater Interfaces ; 12(34): 38700-38707, 2020 Aug 26.
Article in English | MEDLINE | ID: mdl-32803947

ABSTRACT

The utilization of structural water in chemical self-assembly has not only effectively eliminated the negative influences of solvents from solutions or gels but has also provided new insight into the fabrication of new materials in bulk. However, up to now, supramolecular polymerization triggered by structural water has been dominated more by serendipity than rational design. After carefully analyzing the chemical structures of artificial monomers and gaining a deep understanding of the water-triggered assembly process, we report herein the bulk formation of polymeric materials from water and low-molecular weight monomers by rational design instead of serendipity.

19.
Chem Commun (Camb) ; 56(76): 11295-11298, 2020 Sep 24.
Article in English | MEDLINE | ID: mdl-32839794

ABSTRACT

Disclosed here is a new [3+2] annulation of siloxy alkynes that provides robust access to highly enantioenriched, densely-substituted pyrrolidinones and γ-butenolides, whose direct synthesis remains challenging. This process also represents a rare asymmetric synthesis of enantrioenriched molecules from siloxy alkynes.

20.
Angew Chem Int Ed Engl ; 59(45): 20090-20098, 2020 11 02.
Article in English | MEDLINE | ID: mdl-32696545

ABSTRACT

The synthesis of a new tetraborylethylene (TBE) is reported, and its application in the preparation of [4+0]-tetraarylethenes (TAEs) is elucidated. TAEs have widespread applications in material science and supramolecular chemistry due to their aggregation-induced emission (AIE) properties. The divergent and stereoselective synthesis of [3+1]-, [2+2]-, and [2+1+1]-TAEs via multiple couplings of vinylboronates with aryl bromides is demonstrated. These couplings feature a broad substrate scope and excellent functional group compatibility due to mild reaction conditions. Facile access to various tetraarylethenes is provided. This strategy represents an important complement to the conventional methods employed for the synthesis of TAEs, and would be a valuable tool for synthesizing TAE-based molecules useful in functional materials, biological imaging and chemical sensing.

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