Jinbo Hu

Find an error

Name: 胡金波; JinBo Hu

Organization: Chinese Academy of Sciences , China

Department: Shanghai Institute of Organic Chemistry

Title: Researcher/Professor(PhD)

TOPICS

Organic Chemistry

Chemicals
References

Chlorodifluoromethyl aryl ketones and sulfones as difluorocarbene reagents: The substituent effect

Co-reporter:Fei Wang, Laijun Zhang, Ji Zheng, Jinbo Hu

Journal of Fluorine Chemistry 2011 Volume 132(Issue 8) pp:521-528

Publication Date(Web):August 2011

DOI:10.1016/j.jfluchem.2011.05.009

We have investigated the different chlorodifluoromethyl aryl ketones 1a–1g and sulfones 2a–2h as difluorocarbene reagents for O- and N-difluoromethylations. It was found that the sulfone reagents 2 were generally more efficient in difluoromethylation than the ketone reagents 1. Furthermore, while the different substituents on ketone reagents 1 did not show a remarkable impact on the difluoromethylation reaction, the substituent effect on the sulfone reagents 2 was much more significant. Finally, we found that p-chlorophenyl chlorodifluoromethyl sulfone 2d and p-nitrophenyl chlorodifluoromethyl sulfone 2h were among the most powerful difluorocarbene reagents in this category for O-difluoromethylations.Graphical abstractThis paper describes the interesting substitution effect in chlorodifluoromethyl aryl ketones and sulfones as difluoromethylating agents for phenols. It was found that, while the different substitution groups on ketone reagents 1 did not show a remarkable impact on the difluoromethylation reaction, the substitution effect on the sulfone reagents 2 was much more significant. Finally, we figured out that p-chlorophenyl chlorodifluoromethyl sulfone 2d and p-nitrophenyl chlorodifluoromethyl sulfone 2h were among the most powerful difluorocarbene reagents in this category.Highlights► Chlorodifluoromethyl aryl ketones 1 and sulfones 2 were surveyed as:CF2 reagents. ► The substitution groups on reagents 1 and 2 showed different effect on their reactivity. ► Two of the most efficient difluorocarbene reagents in this category have been selected. ► The different substitution effects on 1 and 2 were rationalized.

Difluoromethylation of O-, S-, N-, C-Nucleophiles Using Difluoromethyltri(n-butyl)ammonium Chloride as a New Difluorocarbene Source

Co-reporter:Fei Wang;Weizhou Huang

Chinese Journal of Chemistry 2011 Volume 29( Issue 12) pp:2717-2721

Publication Date(Web):

DOI:10.1002/cjoc.201100325

Abstract

Difluoromethyltri(n-butyl)ammonium chloride 1 was found to be an effective difluorocarbene reagent for O-, S-, N-, C-difluoromethylation under basic conditions. It is particularly remarkable that, when only 1.2 equivalent of reagent 1 was used, the difluoromethylated products were obtained in moderate to excellent yields.

Selective difluoromethylation and monofluoromethylation reactions

Co-reporter:Jinbo Hu, Wei Zhang and Fei Wang

Chemical Communications 2009 (Issue 48) pp:7465-7478

Publication Date(Web):30 Oct 2009

DOI:10.1039/B916463D

The selective introduction of fluorine atom(s) and fluorinated moieties into organic molecules has become an important and fast-growing research field, since fluorine atoms play crucial roles in life science and materials science-related applications. Similar to the trifluoromethyl group, both difluoromethyl and monofluoromethyl groups can often bring about many beneficial effects to the target molecules, and a variety of CF2H- and CH2F-containing pharmaceuticals and agrochemicals have been developed. Among the synthetic methods for CF2H- and CH2F-containing compounds, selective di- and monofluoromethylation (i.e., introduction of CF2H and CH2F groups into organic molecules) represent one of the most straightforward synthetic methods and thus can be conveniently used in the synthetic design. This feature article summarizes the presently known selective difluoromethylation and monofluoromethylation methods, including nucleophilic, electrophilic, and free radical di- and monofluoromethylation reagents and reactions.

N-Tosyl-S-difluoromethyl-S-phenylsulfoximine: A New Difluoromethylation Reagent for S-, N-, and C-Nucleophiles

Co-reporter:Wei Zhang, Fei Wang and Jinbo Hu

Organic Letters 2009 Volume 11(Issue 10) pp:2109-2112

Publication Date(Web):April 15, 2009

DOI:10.1021/ol900567c

The first α-difluoromethyl sulfoximine compound, 2, was successfully prepared by using the copper(II)-catalyzed nitrene transfer reaction. Compound 2 was found to be a novel and efficient difluoromethylation reagent for transferring the CF2H group to S-, N-, and C-nucleophiles. Deuterium-labeling experiments suggest that a difluorocarbene mechanism is involved in the current difluoromethylation reactions.

Brnsted Acid Mediated (sp3)Carbon-Fluorine Bond Activation: Inter- and Intramolecular Arylation of Trifluoromethylated Arenes

Co-reporter:Fei WANG

Chinese Journal of Chemistry 2009 Volume 27( Issue 1) pp:93-98

Publication Date(Web):

DOI:10.1002/cjoc.200990032

Abstract

Trifluoromethanesulfonic acid (triflic acid) was found to be able to efficiently activate the benzylic sp³ C–F bond. Thus, under the catalysis of triflic acid at room temperature, trifluoromethylated arenes readily reacted with benzene to give benzophenones in moderate to good yields. Under similar B?nsted acid catalysis, intramolecular arylation also happened in the cases of some CF₃-arene substrates bearing an additional nucleophilic aryl group. Strong CF···H⁺ interaction or hydrogen bonding, is believed to play an important role in the current Br?nsted acid-mediated C–F bond activation chemistry.

C−F Bond Cleavage by Intramolecular SN2 Reaction of Alkyl Fluorides with O- and N-Nucleophiles

Co-reporter:Laijun Zhang, Wei Zhang, Jun Liu and Jinbo Hu

The Journal of Organic Chemistry 2009 Volume 74(Issue 7) pp:2850-2853

Publication Date(Web):March 5, 2009

DOI:10.1021/jo802819p

The nucleophilic substitution of alkyl fluorides was achieved in the intramolecular reactions with O- and N-nucleophiles. The intramolecular defluorinative cyclization reaction was influenced by the nature of nucleophiles, the size of the ring to be formed, and the comformational rigidity of the precursors. Intermolecular nucleophilic substitution reactions of alkyl fluorides under similar reaction conditions were found to be difficult. The stereochemistry study of the current C−F bond cleavage reaction showed a complete configurational inversion, which supports an intramolecular SN2 reaction mechanism.

Nucleophilic, radical, and electrophilic (phenylsulfonyl)difluoromethylations

Co-reporter:Jinbo Hu

Journal of Fluorine Chemistry 2009 130(12) pp: 1130-1139

Publication Date(Web):

DOI:10.1016/j.jfluchem.2009.05.016

Palladium/acetic acid-catalyzed fluoroalkylation of alkynes with monofluorinated sulfones as pronucleophiles

Co-reporter:Chuanfa Ni, Jinbo Hu

Tetrahedron Letters 2009 50(52) pp: 7252-7255

Publication Date(Web):

DOI:10.1016/j.tetlet.2009.09.126

Free radical (phenylsulfonyl)difluoromethylation of alkynes with PhSO2CF2I reagent: stereoselective preparation of PhSO2CF2- and CF2H-substituted alkenes

Co-reporter:Ya Li, Huaifeng Li, Jinbo Hu

Tetrahedron 2009 65(2) pp: 478-483

Publication Date(Web):

DOI:10.1016/j.tet.2008.11.011

Highly Stereoselective Synthesis of Monofluoroalkenes from -Fluorosulfoximines and Nitrones

Co-reporter:Wei Zhang;Weizhou Huang Dr.

Angewandte Chemie International Edition 2009 Volume 48( Issue 52) pp:9858-9861

Publication Date(Web):

DOI:10.1002/anie.200905077

Highly Stereoselective Synthesis of Monofluoroalkenes from -Fluorosulfoximines and Nitrones

Co-reporter:Wei Zhang;Weizhou Huang Dr.

Angewandte Chemie 2009 Volume 121( Issue 52) pp:10042-10045

Publication Date(Web):

DOI:10.1002/ange.200905077

Synthesis of Fluorinated β-Ketosulfones and gem-Disulfones by Nucleophilic Fluoroalkylation of Esters and Sulfinates with Di- and Monofluoromethyl Sulfones

Co-reporter:Chuanfa Ni, Laijun Zhang and Jinbo Hu

The Journal of Organic Chemistry 2009 Volume 74(Issue 10) pp:3767-3771

Publication Date(Web):April 17, 2009

DOI:10.1021/jo900320b

An efficient and practically useful method for the preparation of α-functionalized mono- and difluoro(phenylsulfonyl)methanes by using a nucleophilic fluoroalkylation methodology was developed. α,α-Difluoro-β-ketosulfones, α-monofluoro-β-ketosulfones, and α-fluoro disulfones were successfully prepared in excellent yields by nucleophilic fluoroalkylation of esters and sulfinates with PhSO2CF2H and PhSO2CH2F reagents.

Chlorodifluoromethyl phenyl sulfone: a novel non-ozone-depleting substance-based difluorocarbene reagent for O- and N-difluoromethylations

Co-reporter:Ji Zheng, Ya Li, Laijun Zhang, Jinbo Hu, Gerrit Joost Meuzelaar and Hans-Jürgen Federsel

Chemical Communications 2007 (Issue 48) pp:5149-5151

Publication Date(Web):16 Oct 2007

DOI:10.1039/B713156A

Chlorodifluoromethyl phenyl sulfone, a previously unknown compound that can be readily prepared from non-ODS-based precursors, was found to act as a robust difluorocarbene reagent for O- and N-difluoromethylations.

Nucleophilic (phenylsulfinyl)difluoromethylation of carbonyl compounds with difluoromethyl phenyl sulfoxide

Co-reporter:Lingui Zhu, Ya Li, Chuanfa Ni, Jinbo Hu, Petr Beier, Ying Wang, G.K. Surya Prakash, George A. Olah

Journal of Fluorine Chemistry 2007 Volume 128(Issue 10) pp:1241-1247

Publication Date(Web):October 2007

DOI:10.1016/j.jfluchem.2007.05.003

We have successfully achieved nucleophilic (phenylsulfinyl)difluoromethylation of both enolizable and non-enolizable aldehydes and ketones by using difluoromethyl phenyl sulfone (1) as the fluoroalkylating agent. Although the chemical yields of the reactions are good to excellent, the observed diastereoselectivity is poor (dr = 1:1.04–2.03). The present synthetic methodology provides a convenient alternative for the preparation of α-(phenylsulfinyl)difluoromethylated carbinols that were previously synthesized via a two-step procedure.

Stereoselective Difluoromethylenation Using Me3SiCF2SPh: Synthesis of Chiral 2,4-Disubstituted 3,3-Difluoropyrrolidines

Co-reporter:Ya Li Dr.

Angewandte Chemie 2007 Volume 119(Issue 14) pp:

Publication Date(Web):27 FEB 2007

DOI:10.1002/ange.200604783

Ein Radikalsynthon: Die nucleophile (Phenylthio)difluormethylierung von (R)-N-(tert-Butylsulfinyl)iminen mit 1, einem Difluormethylenradikalanion-Äquivalent, liefert die Produkte in guten Ausbeuten und mit hoher Diastereoselektivität (d.r.≥98:2). Die erhaltenen PhSCF₂-substituierten Sulfinamide können durch intramolekulare radikalische Cyclisierung in chirale 2,4-trans-disubstituierte 3,3-Difluorpyrrolidine überführt werden.

A Remarkably Efficient Fluoroalkylation of Cyclic Sulfates and Sulfamidates with PhSO2CF2H: Facile Entry into β-Difluoromethylated or β-Difluoromethylenated Alcohols and Amines

Co-reporter:Chuanfa Ni;Jun Liu;Laijun Zhang Dr.

Angewandte Chemie International Edition 2007 Volume 46(Issue 5) pp:

Publication Date(Web):13 DEC 2006

DOI:10.1002/anie.200603983

On the fluor: Highly regioselective nucleophilic difluoromethylation of 1,2-cyclic sulfates and sulfamidates leads after selective desulfonylation to β-difluoromethylated and β-difluoromethylenated alcohols and amines (see scheme), which are highly useful building blocks in the life sciences.

A Remarkably Efficient Fluoroalkylation of Cyclic Sulfates and Sulfamidates with PhSO2CF2H: Facile Entry into β-Difluoromethylated or β-Difluoromethylenated Alcohols and Amines

Co-reporter:Chuanfa Ni;Jun Liu;Laijun Zhang Dr.

Angewandte Chemie 2007 Volume 119(Issue 5) pp:

Publication Date(Web):13 DEC 2006

DOI:10.1002/ange.200603983

Fluor kommt rein: Die hoch regioselektive nucleophile Difluormethylierung von cyclischen 1,2-Sulfaten und -Sulfamidaten liefert nach der selektiven Desulfonylierung β-difluormethylierte und β-difluormethylenierte Alkohole bzw. Amine (siehe Schema), äußerst nützliche Bausteine für die Biowissenschaften.

Stereoselective Difluoromethylenation Using Me3SiCF2SPh: Synthesis of Chiral 2,4-Disubstituted 3,3-Difluoropyrrolidines

Co-reporter:Ya Li Dr.

Angewandte Chemie International Edition 2007 Volume 46(Issue 14) pp:

Publication Date(Web):27 FEB 2007

DOI:10.1002/anie.200604783

A radical synthon: Nucleophilic (phenylthio)difluoromethylation of (R)-N-(tert-butylsulfinyl)imines with 1, a difluoromethylene radical anion equivalent, afforded the corresponding products in good yields and with high diastereoselectivity (d.r.≥98:2). The resulting PhSCF₂-containing sulfinamides can be further transformed into chiral 2,4-trans-disubstituted 3,3-difluoropyrrolidines through an intramolecular radical cyclization methodology.

Facile Synthesis of Chiral α-Difluoromethyl Amines from N-(tert-Butylsulfinyl)aldimines

Co-reporter:Ya Li Dr.

Angewandte Chemie 2005 Volume 117(Issue 36) pp:

Publication Date(Web):8 SEP 2005

DOI:10.1002/ange.200501769

Die nucleophile (Phenylsulfonyl)difluormethylierung von (R)-(N-tert-Butylsulfinyl)aldiminen mit (Difluormethyl)phenylsulfon verläuft mit ausgezeichneten Ausbeuten und hoher Diastereoselektivität (siehe Schema). Das unproblematische Entschützen von tert-Butylsulfinyl- und Phenylsulfonylgruppen liefert die gewünschten α-Difluormethylamine in hoher Enantiomerenreinheit.

Facile Synthesis of Chiral α-Difluoromethyl Amines from N-(tert-Butylsulfinyl)aldimines

Co-reporter:Ya Li Dr.

Angewandte Chemie International Edition 2005 Volume 44(Issue 36) pp:

Publication Date(Web):8 SEP 2005

DOI:10.1002/anie.200501769

Nucleophilic (phenylsulfonyl)difluoromethylation of (R)-(N-tert-butylsulfinyl)aldimines with difluoromethyl phenyl sulfone affords the corresponding products in excellent yields and with high diastereoselectivity (see scheme). The facile and convenient deprotection of both tert-butylsulfinyl and phenylsulfonyl groups affords the target α-difluoromethyl amines with high enantiomeric purity.

Chlorodifluoromethyl phenyl sulfone: a novel non-ozone-depleting substance-based difluorocarbene reagent for O- and N-difluoromethylations

Co-reporter:Ji Zheng, Ya Li, Laijun Zhang, Jinbo Hu, Gerrit Joost Meuzelaar and Hans-Jürgen Federsel

Chemical Communications 2007(Issue 48) pp:NaN5151-5151

Publication Date(Web):2007/10/16

DOI:10.1039/B713156A

Selective difluoromethylation and monofluoromethylation reactions

Co-reporter:Jinbo Hu, Wei Zhang and Fei Wang

Chemical Communications 2009(Issue 48) pp:NaN7478-7478

Publication Date(Web):2009/10/30

DOI:10.1039/B916463D