Boron tribromide as a reagent for anti-Markovnikov addition of HBr to cyclopropanes

Matthew H. Gieuw; Shuming Chen; Zhihai Ke; K. N. Houk; Ying-Yeung Yeung

doi:10.1039/d0sc02567d

Harnessing Applied Potential: The Anti-Markovnikov Hydrocarboxylation of Substituted Olefins

10.26434/chemrxiv.7985300.v2 ◽

2019 ◽

Author(s):

Anas Alkayal ◽

Volodymyr Tabas ◽

Andrei V. Malkov ◽

Benjamin Buckley

Keyword(s):

Carboxylic Acid ◽

Applied Potential ◽

Markovnikov Addition

<div>The construction of carboxylic acid compounds in a selective fashion, from low value materials such as alkenes remains a long-standing challenge to synthetic chemists. In particular, anti-Markovnikov addition to styrenes are underdeveloped. Herein we report a new electrosynthetic approach to the selective hydrocarboxylation of substituted alkenes.</div>

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Harnessing Applied Potential: The Anti-Markovnikov Hydrocarboxylation of Substituted Olefins

10.26434/chemrxiv.7985300.v1 ◽

2019 ◽

Author(s):

Anas Alkayal ◽

Volodymyr Tabas ◽

Andrei V. Malkov ◽

Benjamin Buckley

Keyword(s):

Carboxylic Acid ◽

Applied Potential ◽

Markovnikov Addition

<div>The construction of carboxylic acid compounds in a selective fashion, from low value materials such as alkenes remains a long-standing challenge to synthetic chemists. In particular, anti-Markovnikov addition to styrenes are underdeveloped. Herein we report a new electrosynthetic approach to the selective hydrocarboxylation of substituted alkenes.</div>

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Fluorinated tricyclic neuroleptics with prolonged action: 8-Methoxy, 8-ethoxy, 8-ethylthio and 8-hydroxy derivatives of 3-fluoro-10-(4-methylpiperazino)-10,11-dihydrodibenzo[b,f]thiepin

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19821382 ◽

1982 ◽

Vol 47 (5) ◽

pp. 1382-1391 ◽

Cited By ~ 2

Author(s):

Jiří Jílek ◽

Josef Pomykáček ◽

Jiřina Metyšová ◽

Miroslav Protiva

Keyword(s):

Acetic Acid ◽

Polyphosphoric Acid ◽

Prolonged Action ◽

Substitution Reactions ◽

Methoxy Derivative ◽

Chloro Derivatives ◽

Boron Tribromide ◽

Derivatives Of ◽

Central Depressant ◽

Boiling Toluene

Acids IIa-c were prepared by reactions of (4-fluoro-2-iodophenyl)acetic acid with 4-methoxythiophenol, 4-ethoxythiophenol and 4-(ethylthio)thiophenol and cyclized with polyphosphoric acid in boiling toluene to dibenzo[b,f]thiepin-10(11H)-ones IIIa-c. Reduction with sodium borohydride afforded the alcohols IVa-c which were treated with hydrogen chloride and gave the chloro derivatives Va-c. Substitution reactions with 1-methylpiperazine resulted in the title compounds Ia-c out of which the methoxy derivative Ia was transformed by demethylation with boron tribromide to the phenol Id. Compounds Ia-d are very potent neuroleptics exhibiting a clear prolongation of the central depressant and some prolongation of the cataleptic activity.

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Reactivity of Sodium Hexaethyl-2,4-dicarba-nido-hexaborate(1-)

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19990977 ◽

1999 ◽

Vol 64 (6) ◽

pp. 977-985 ◽

Cited By ~ 17

Author(s):

Bernd Wrackmeyer ◽

Hans-Jörg Schanz ◽

Wolfgang Milius ◽

Catherine McCammon

Keyword(s):

Mössbauer Spectroscopy ◽

Nmr Spectroscopy ◽

Structural Analysis ◽

Hydrogen Atom ◽

Mossbauer Spectroscopy ◽

Sandwich Complex ◽

X Ray ◽

Bromo Derivative ◽

Boron Tribromide ◽

C Nmr

Sodium hexaethyl-2,4-dicarba-nido-hexaborate(1-) (6), available from hexaethyl-2,4-dicarba- nido-hexaborane(8) (4) by deprotonation, reacts with deuterated methanol, CD3OD, to give back 4 without H/D exchange of the B-H-B hydrogen atom. The reaction of 6 with diethylboron chloride, Et2BCl, affords hexaethyl-2,4-dicarba-closo-hexaborane(6) (7), the first example of a peralkylated carborane of this type. In contrast, the reaction of 6 with boron tribromide, BBr3, leads mainly to 2,3,4,5,6,7-hexaethyl-2,4-dicarba-closo-heptaborane(7) (8), together with the corresponding 1-bromo derivative (9) and the closo-carborane 7 as side products. The reaction of two equivalents of 6 with FeCl2 gives the air-stable sandwich complex bis[hexaethyl-2,4-dicarba-nido-hexaborate(1-)]iron 10 which was characterised by X-ray structural analysis. All products were characterised by 1H, 11B and 13C NMR spectroscopy, and 57Fe Mössbauer spectroscopy was used to study 10.

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ChemInform Abstract: Rhodium-Catalyzed anti-Markovnikov Addition of Triphenylphosphine to 1,3-Dienes - A Novel Method to Separate Pure (Z)-1,3-Alkadienes from Isomeric Mixtures.

ChemInform ◽

10.1002/chin.200233199 ◽

2010 ◽

Vol 33 (33) ◽

pp. no-no

Author(s):

Mieko Arisawa ◽

Ryohei Momozuka ◽

Masahiko Yamaguchi

Keyword(s):

Novel Method ◽

Markovnikov Addition ◽

Isomeric Mixtures

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Rhodium-Catalyzed Selectiveanti-Markovnikov Addition of Carboxylic Acids to Alkynes

Organic Letters ◽

10.1021/ol102365e ◽

2010 ◽

Vol 12 (23) ◽

pp. 5498-5501 ◽

Cited By ~ 57

Author(s):

Alexandre Lumbroso ◽

Nicolas R. Vautravers ◽

Bernhard Breit

Keyword(s):

Carboxylic Acids ◽

Markovnikov Addition

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Three-component reaction between secondary phosphine sulfides, elemental selenium and vinyl ethers: the first examples of Markovnikov addition of thioselenophosphinic acids to double bond

Tetrahedron ◽

10.1016/j.tet.2013.05.038 ◽

2013 ◽

Vol 69 (30) ◽

pp. 6185-6195 ◽

Cited By ~ 4

Author(s):

Ludmila A. Oparina ◽

Alexander V. Artem'ev ◽

Oksana V. Vysotskaya ◽

Nikita A. Kolyvanov ◽

Irina Yu. Bagryanskaya ◽

...

Keyword(s):

Double Bond ◽

Elemental Selenium ◽

Secondary Phosphine ◽

Vinyl Ethers ◽

Three Component Reaction ◽

Markovnikov Addition

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Preparation of Some 2-(Methoxyphenyl)-2H-benzotriazoles and the Corresponding Hydroxyphenyl Compounds

Australian Journal of Chemistry ◽

10.1071/ch9871663 ◽

1987 ◽

Vol 40 (10) ◽

pp. 1663 ◽

Cited By ~ 3

Author(s):

J Rosevear ◽

JFK Wilshire

Keyword(s):

Acetic Acid ◽

Good Yield ◽

Hydrobromic Acid ◽

Methoxy Group ◽

Methylene Chloride ◽

Thiourea Dioxide ◽

Boron Tribromide

The reaction of several substituted o- nitronitrosobenzenes with O- and p- anisidine , and 2,4- dimethoxyaniline in acetic acid gives in good yield the corresponding enitroazobenzenes which are readily reduced with thiourea dioxide ( formamidinesulfinic acid) to the corresponding 2-(methoxypheny1)-2H-benzotriazoles, demethylation of which furnished the corresponding 2- (hydroxypheny1)-2H-benzotriazoles. Demethylation of the dimethoxy derivatives was best accomplished with boron tribromide in methylene chloride, the methoxy group located ortho to the benzotriazole ring being demethylated more readily than is the para-methoxy group. The reaction of enitroazobenzenes containing a methoxy group with hydrobromic acid in acetic acid results in cleavage of the azo bond and also partial bromination to give o- nitroaniline and some of its brominated derivatives.

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