32281-97-3

Usage

Chemical Properties

White to yellow to tan powder or crystal

InChI:InChI=1/C10H9BrO/c11-8-5-4-7-2-1-3-10(12)9(7)6-8/h4-6H,1-3H2

Synthetic route

4-(4-bromophenyl)butanoic acid (35656-89-4) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
With PPA at 90℃; for 0.25h;	100%
With PPA at 90℃; for 2h;	95%
With phosphorus pentoxide In toluene at 110℃; for 2h; Temperature; Time;	95%

7-bromo-1,2,3,4-tetrahydronaphthalen-1-ol (75693-15-1) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
With acetic acid; 1,1'-(phenyl-l3-iodanediyl)bis(pyridinium)trifluoromethanesulfonate In 1,2-dichloro-ethane at 60℃; for 1.5h; Inert atmosphere; Molecular sieve; chemoselective reaction;	95%
With pivalaldehyde In toluene at 40℃; for 0.5h; Flow reactor;	90%

4-(4-bromophenyl)-butyryl chloride (6628-03-1) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
With Fe-Al-MCM-41 molecular sieve In toluene at 60℃; for 18h; Green chemistry;	84%
With carbon disulfide; aluminium trichloride at 0℃;

3,4-dihydronaphthalene-1(2H)-one (529-34-0) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + 5-bromo-1-tetralone (68449-30-9)

Conditions	Yield
With bromine; aluminum (III) chloride at 80℃;	A 42% B 51%
With aluminum (III) chloride; bromine at 75 - 80℃; for 0.55h;	A 42% B 51%
Stage #1: 3,4-dihydronaphthalene-1(2H)-one With aluminum (III) chloride at 75 - 80℃; for 0.216667h; Stage #2: With bromine for 0.333333h;	A 42% B 51%

3,4-dihydronaphthalene-1(2H)-one (529-34-0) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
Stage #1: 3,4-dihydronaphthalene-1(2H)-one; aluminum (III) chloride at 0 - 90℃; for 0.916667h; Stage #2: With bromine at 90℃; for 1h;	40%
With bromine; aluminum (III) chloride

3,4-dihydronaphthalene-1(2H)-one (529-34-0) → Reaxys ID: 11943741 + 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + 5-bromo-1-tetralone (68449-30-9)

Conditions	Yield
Stage #1: 3,4-dihydronaphthalene-1(2H)-one With aluminum (III) chloride Under N2; Stage #2: With bromine at 80℃; for 0.0833333h;	A 20.9% B 35.8% C 28.3%

bromobenzene (108-86-1) + (hexacarbonyl)chromium → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 85 percent / aluminum chloride / 1,2-dichloro-benzene / 6 h / 83 °C 2: 82 percent / KOH; hydrazine monohydrate / triethylene glycol / 90 - 200 °C 3: 75 percent / polyphosphoric acid / 1 h / 80 °C View Scheme

4-(4-bromophenyl)-4-oxo-butyric acid (6340-79-0) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 82 percent / KOH; hydrazine monohydrate / triethylene glycol / 90 - 200 °C 2: 75 percent / polyphosphoric acid / 1 h / 80 °C View Scheme
Multi-step reaction with 2 steps 1: 90 percent / potassium hydroxide; hydrazine / triethylene glycol / 2 h / Heating 2: 83 percent / polyphosphoric acid / 0.33 h / 90 °C View Scheme
Multi-step reaction with 2 steps 1: 98 percent / KOH; H2NNH2 / triethylene glycol / 2 h / 200 °C 2: 95 percent / polyphosphoric acid / 2 h / 90 °C View Scheme

4-(4-bromophenyl)-3-butenoic acid → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: hydrogen / Pd/C / tetrahydrofuran / 3 h / 20 °C / 760.21 Torr 2: P2O5; methanesulfonic acid / 12 h / 20 °C View Scheme

C22H35BrO2Sn → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: hydrochloric acid / H2O / 0.25 h / 20 °C 2: hydrogen / Pd/C / tetrahydrofuran / 3 h / 20 °C / 760.21 Torr 3: P2O5; methanesulfonic acid / 12 h / 20 °C View Scheme

bromobenzene (108-86-1) + Mg → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 85 percent / AlCl3 / 1,2-dichloro-benzene / 7 h / 95 °C 2: 98 percent / KOH; H2NNH2 / triethylene glycol / 2 h / 200 °C 3: 95 percent / polyphosphoric acid / 2 h / 90 °C View Scheme

bromobenzene (108-86-1) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 69 percent / AlCl3 / cyclohexane / 0.25 h / Heating 2: 94 percent / Clemmensen procedure 3: 100 percent / PPA / 0.25 h / 90 °C View Scheme
Multi-step reaction with 4 steps 1: aluminium chloride 2: amalgamated zinc; aqueous hydrochloric acid; toluene / weiteres Reagens: Essigsaeure 3: thionyl chloride 4: AlCl3; carbon disulfide / 0 °C View Scheme
Multi-step reaction with 3 steps 1.1: aluminum (III) chloride / nitrobenzene / 0.5 h / 20 °C 1.2: 60 °C 2.1: palladium 10% on activated carbon; hydrogen / acetic acid / 70 °C 3.1: polyphosphoric acid / 90 °C View Scheme

bromobenzene (108-86-1) + potassium biphenylolate-(4) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: AlCl3 2: Zn-Hg, aq. HCl 3: polyphosphoric acid View Scheme
Multi-step reaction with 3 steps 1: AlCl3 2: N2H4, KOH / bis-(2-hydroxy-ethyl) ether 3: polyphosphoric acid View Scheme

4-(3-bromophenyl)-butyric acid (899350-32-4) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
With polyphosphoric acid at 90℃;

4-(3-bromophenyl)-4-oxo-butyric acid (62903-13-3) → 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: palladium 10% on activated carbon; hydrogen / acetic acid / 70 °C 2: polyphosphoric acid / 90 °C View Scheme

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → 7-bromo-1,2,3,4-tetrahydronaphthalen-1-ol (75693-15-1)

Conditions	Yield
With sodium tetrahydroborate In methanol; dichloromethane at 20 - 23℃; for 1h;	100%
With methanol; sodium tetrahydroborate In dichloromethane at 20℃; for 1h;	100%
With methanol; sodium tetrahydroborate at 20℃;	92%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → 7-bromo-N-hydroxy-3,4-dihydronaphthalen-1(2H)-imine (877263-91-7)

Conditions	Yield
With hydroxylamine hydrochloride; sodium acetate In ethanol for 2h; Heating / reflux;	100%
With hydroxylamine hydrochloride; sodium acetate In ethanol; water at 80℃; for 0.75h;	95%
With hydroxylamine hydrochloride; sodium acetate In ethanol at 80℃; for 2h;	93%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + methyl iodide (74-88-4) → 7-bromo-2,2-dimethyl-3,4-dihydronaphthalen-1(2H)-one (148925-37-5)

Conditions	Yield
In benzene	100%
Stage #1: 7-bromo-3,4-dihydro-2H-naphthalen-1-one With potassium tert-butylate In tetrahydrofuran for 6h; Reflux; Stage #2: methyl iodide at 20 - 50℃; for 3.25h;	95%
With sodium hydride In benzene Heating;	90%
Stage #1: 7-bromo-3,4-dihydro-2H-naphthalen-1-one With sodium hydride In tetrahydrofuran for 1h; Cooling with ice; Stage #2: methyl iodide In tetrahydrofuran at 20℃; for 16h;	86%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → C10H11BrN2 (1260541-32-9)

Conditions	Yield
With hydrazine hydrate In ethanol for 2h; Reflux;	100%
With hydrazine hydrate; triethylamine In water at 95℃; for 1h;
With hydrazine hydrate In methanol at 80℃; for 3h; Sealed tube; Inert atmosphere; Schlenk technique;

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + carbonic acid dimethyl ester (616-38-6) → 7-Brom-2-methoxycarbonyl-1-tetralon

Conditions	Yield
With sodium hydride In methanol; toluene at 90℃; for 2h;	100%
With potassium tert-butylate; sodium hydride at 0℃; Inert atmosphere;
With sodium hydride In mineral oil for 12h; Reflux;

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → 1,7-dibromo-1,2,3,4-tetrahydronaphthalene

Conditions	Yield
Stage #1: 7-bromo-3,4-dihydro-2H-naphthalen-1-one With sodium tetrahydroborate; ethanol at 20℃; Stage #2: With phosphorus tribromide In dichloromethane at 0 - 20℃;	100%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + ethylene glycol (107-21-1) → 7-Bromo-1,2,3,4-tetrahydronaphthalene-1-spiro-2'-(1',3'-dioxacyclopentane) (111773-13-8)

Conditions	Yield
With toluene-4-sulfonic acid In benzene at 105℃; for 48h;	99%
With toluene-4-sulfonic acid In benzene for 24h; Heating / reflux; Dean-Stark apparatus;	99%
With toluene-4-sulfonic acid In toluene for 12h; Heating;	92%
With VO(OTf)2*5H2O In benzene for 12h; Reflux;	83%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → 7-bromo-1,2,3,4-tetrahydronaphthalen-1-ol (676133-23-6)

Conditions	Yield
With dimethylsulfide borane complex; (S)-1-methyl-3,3-diphenyl-hexahydropyrrolo[1,2-c][1,3,2]oxazaborole In tetrahydrofuran; toluene at -25 - -15℃; for 6.3h; 4A molecular sieves;	98%
Stage #1: 7-bromo-3,4-dihydro-2H-naphthalen-1-one; dimethylsulfide borane complex; (S)-1-methyl-3,3-diphenyl-hexahydropyrrolo[1,2-c][1,3,2]oxazaborole In tetrahydrofuran; toluene at -25 - -15℃; for 1.33333h; Stage #2: With methanol In tetrahydrofuran; toluene at -20 - 20℃; for 16h;	98%
With hydrogen; C43H45ClN4Ru; sodium t-butanolate In isopropyl alcohol at 22℃; under 7500.75 Torr; for 24h; Autoclave; enantioselective reaction;	98%

2,2,2-trifluoroethyl acrylate (407-47-6) + 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → C15H12BrF3O3

Conditions	Yield
With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; copper(II) acetate monohydrate In tert-Amyl alcohol at 20 - 100℃; for 12.33h; Schlenk technique; Sealed tube; regioselective reaction;	98%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + benzaldehyde N-boc imine (150884-50-7) → tert-butyl ((S)-((R)-7-bromo-1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)(phenyl)methyl)carbamate

Conditions	Yield
With 1,2,2,6,6-pentamethylpiperidine; C62H26B2F26 In toluene at 22℃; for 20h; Sealed tube; Inert atmosphere; enantioselective reaction;	98%

di-tert-butyl-diazodicarboxylate (870-50-8) + 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → C20H27BrN2O5

Conditions	Yield
With (R,R)-(-)-2,6-bis[2-(hydroxyldiphenylmethyl)-1-pyrrolidinyl-methyl]-4-methylphenole; diethylzinc In tetrahydrofuran at 23℃; Molecular sieve; enantioselective reaction;	98%

chloro-trimethyl-silane (75-77-4) + 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → ((7-bromo-3,4-dihydronaphthalen-1-yl)oxy)trimethylsilane (309929-09-7)

Conditions	Yield
Stage #1: 7-bromo-3,4-dihydro-2H-naphthalen-1-one With triethylamine at 20℃; for 0.25h; Inert atmosphere; Stage #2: chloro-trimethyl-silane for 0.666667h; Inert atmosphere; Stage #3: With sodium iodide In acetonitrile at 40℃; for 2h;	96%
Stage #1: 7-bromo-3,4-dihydro-2H-naphthalen-1-one With lithium diisopropyl amide In tetrahydrofuran; hexane at -78℃; for 2h; Metallation; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Substitution; Silylation;	92%
With triethylamine; sodium iodide In acetonitrile at 20℃; for 0.5h; Inert atmosphere;	69%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + 4-bromo-benzaldehyde (1122-91-4) → (E)-7-bromo-2-(4-bromobenzylidene)-1-tetralone (1039020-10-4)

Conditions	Yield
With potassium hydroxide In methanol at 20℃; for 48h;	96%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + 4-Phenylbenzaldehyde (3218-36-8) → (E)-2-(biphenyl-4-ylmethylene)-7-bromo-1-tetralone (1039020-19-3)

Conditions	Yield
With potassium hydroxide In methanol at 20℃; for 48h;	96%

2-diazo-3-phenyl-propionic acid ethyl ester (15626-54-7) + 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → ethyl 2-(2-(7-bromo-1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)hydrazono)-3-phenylpropanoate

Conditions	Yield
Stage #1: 7-bromo-3,4-dihydro-2H-naphthalen-1-one With C43H64N4O4; lithium carbonate; scandium tris(trifluoromethanesulfonate) In dichloromethane at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: 2-diazo-3-phenyl-propionic acid ethyl ester In dichloromethane at 20℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	96%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + 4-methoxy-benzaldehyde (123-11-5) → C18H15BrO2

Conditions	Yield
With potassium hydroxide In methanol; water at 25℃; for 28h;	96%

N,N-phenylbistrifluoromethane-sulfonimide (37595-74-7) + 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → 7-bromo-3,4-dihydronaphthalen-1-yl trifluoromethanesulfonate

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran; toluene at -78 - 20℃; Inert atmosphere;	96%

carbon monoxide (201230-82-2) + 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + butan-1-ol (71-36-3) → 7-butoxycarbonyl-α-tetralone

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride In triethylamine; N,N-dimethyl-formamide at 80℃; under 2068.6 Torr;	95%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → 6-bromo-1,2,3,4-tetrahydronaphthalene (6134-56-1)

Conditions	Yield
With triethylsilane In trifluoroacetic acid at 20℃;	95%
With triethylsilane; trifluoroacetic acid at 20 - 50℃; for 4h;	94%
With indium(III) chloride; dimethylmonochlorosilane In dichloromethane at 0℃; for 14h;	32%
With triethylsilane; trifluoroacetic acid at 0 - 35℃;

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → (E)-7-bromo-3,4-dihydronaphthalene-1(2H)-oneoxime

Conditions	Yield
With hydroxylamine hydrochloride; sodium acetate In ethanol for 2h; Reflux;	95%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + dimethyl sulfoxide (67-68-5) → 2-(7-bromo-1,4-naphthoquinone)methyl sulfide

Conditions	Yield
With iodine at 80℃; for 12h; Inert atmosphere;	95%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → 7-bromo-1-chloro-3,4-dihydronaphthalene-2-aldehyde (283177-40-2)

Conditions	Yield
With trichlorophosphate In Trichloroethylene at 60 - 70℃; for 6h; Chlorination;	94%
With trichlorophosphate Vilsmeier-Haack Formylation;

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + Methyltriphenylphosphonium bromide (1779-49-3) → 7-bromo-1-methylene-1,2,3,4-tetrahydronaphthalene (740842-57-3)

Conditions	Yield
Stage #1: Methyltriphenylphosphonium bromide With potassium tert-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 7-bromo-3,4-dihydro-2H-naphthalen-1-one In tetrahydrofuran at 20℃; Inert atmosphere;	93%
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at -45℃; for 1h; Stage #2: 7-bromo-3,4-dihydro-2H-naphthalen-1-one In tetrahydrofuran at -45 - 20℃;	52%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) → 7-Bromo-1,2,3,4-tetrahydronaphthalene-1-spiro-2'-(1',3'-dioxacyclopentane) (111773-13-8)

Conditions	Yield
With toluene-4-sulfonic acid In toluene Dean Stark;	92%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + benzaldehyde (100-52-7) → 7-benzylidene-2-bromo-α-tetralone (116047-27-9)

Conditions	Yield
With potassium hydroxide In methanol at 20℃; for 48h;	92%
With potassium hydroxide In methanol; water at 20℃; for 12h;	91%

potassium cyanide + 7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + ammonium carbonate (506-87-6) → 7'-bromo-3',4'-dihydro-2'H-spiro[imidazolidine-4,1'-naphthalene]-2,5-dione (1338093-88-1)

Conditions	Yield
Stage #1: potassium cyanide; 7-bromo-3,4-dihydro-2H-naphthalen-1-one; ammonium carbonate With sodium hydrogensulfite In ethanol at 130℃; for 24h; Stage #2: With hydrogenchloride In ethanol; water pH=~ 2;	92%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + N-(but-3-en-1-yloxy)carbamic acid 1,1-dimethylethyl ester (635757-93-6) → C19H25NO4

Conditions	Yield
With bis(3,5,3′,5′-dimethoxydibenzylideneacetone)palladium(0); C42H68NO3PS; caesium carbonate In tert-butyl methyl ether at 30℃; for 48h; Inert atmosphere; enantioselective reaction;	91%

7-bromo-3,4-dihydro-2H-naphthalen-1-one (32281-97-3) + toluene-4-sulfonic acid hydrazide (1576-35-8) → C17H17BrN2O2S

Conditions	Yield
With toluene-4-sulfonic acid In methanol for 7h;	90%

Upstream product

• 6628-03-1 4-(4-bromophenyl)-butyryl chloride 
• 35656-89-4 4-(4-bromophenyl)butanoic acid 
• 108-86-1 bromobenzene 
• 529-34-0 3,4-dihydronaphthalene-1(2H)-one 
• 899350-32-4 4-(3-bromophenyl)-butyric acid 
• 62903-13-3 4-(3-bromophenyl)-4-oxo-butyric acid 
• 75693-15-1 7-bromo-1,2,3,4-tetrahydronaphthalen-1-ol 
• 6340-79-0 4-oxo-4-(4-bromophenyl)butanoic acid 

Downstream Products

• 75693-15-1 7-bromo-1,2,3,4-tetrahydronaphthalen-1-ol 
• 75693-17-3 bromo-7 dihydro-3,4 naphthalene 
• 283177-40-2 7-bromo-1-chloro-3,4-dihydronaphthalene-2-aldehyde 
• 914262-79-6 2-(2-cyano-3,4-dihydronaphthalen-7-yl)-5-(4-cyanophenyl)furan 
• 922715-01-3 (8-bromo-5,6-dihydro-naphthalen-2-yl)-triphenyl-silane 
• 914336-50-8 2-(2-N-hydroxyamidino-3,4-dihydronaphthalen-7-yl)-5-(4-N-hydroxyamidinophenyl)furan 
• 922715-00-2 C₃₄H₂₈O₂Si 
• 33295-35-1 2-bromo-8-methylnaphthalene 
• 332359-30-5 9-iodo-1-(4-methoxybenzyl)-3-methyl-3,4,5,6-tetrahydro-1H-benzo[h]quinolin-2-one 
• 709648-30-6 2-(1-(4-methoxybenzyl)-3-methyl-2-oxo-1,2,3,4,5,6-hexahydrobenzo[h]quinolin-9-yl)malonic acid diethyl ester 
• 309929-10-0 [2S,2(2R,4R)]-7-Bromo-2-{4-ethyl-3-[(4-methylbenzene)sulfonyl]-1,3-oxazolidin-2-yl}-1,2,3,4-tetrahydro-1-naphthalenone 
• 309929-11-1 [2R,2(2R,4R)]-7-Bromo-2-{4-ethyl-3-[(4-methylbenzene)sulfonyl]-1,3-oxazolidin-2-yl}-1,2,3,4-tetrahydro-1-naphthalenone 
• 309929-14-4 (2R,4R)-2-((R)-7-Bromo-1-methylene-1,2,3,4-tetrahydro-naphthalen-2-yl)-4-ethyl-3-(toluene-4-sulfonyl)-oxazolidine 

Relevant academic research and scientific papers

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The site-selective and chemoselective functionalization of alcohols in complex polyols remains a formidable synthetic challenge. Whereas significant advancements have been made in selective derivatization at the oxygen center, chemoselective oxidation to the corresponding carbonyls is less developed. In cyclic systems, whereas the selective oxidation of axial alcohols is well known, a complementary equatorial selective process has not yet been reported. Herein we report the utility of nitrogen-ligated (bis)cationic λ3-iodanes (N-HVIs) for alcohol oxidation and their unprecedented levels of selectivity for the oxidation of equatorial over axial alcohols. The conditions are mild, and the simple pyridine-ligated reagent (Py-HVI) is readily synthesized from commercial PhI(OAc)2 and can be either isolated or generated in situ. Conformational selectivity is demonstrated in both flexible 1,2-substituted cyclohexanols and rigid polyol scaffolds, providing chemists with a novel tool for chemoselective oxidation.

Synthesis of Novel Pterocarpen Analogues via [3?+?2] Coupling-Elimination Cascade of α,α-Dicyanoolefins with Quinone Monoimines

By employing triethylamine as a catalyst, [3?+?2] coupling-elimination cascade of α,α-dicyanoolefins with quinone monoimines was realized. The reactions afforded various novel pterocarpen analogues with generally moderate yields (up to 75%). In addition, a plausible reaction mechanism was proposed.

Visible-light-induced oxidation/[3 + 2] cycloaddition/oxidative aromatization to construct benzo[ a]carbazoles from 1,2,3,4-tetrahydronaphthalene and arylhydrazine hydrochlorides

An efficient synthesis of benzo[a]carbazoles via visible-light-induced tandem oxidation/[3 + 2] cycloaddition/oxidative aromatization reactions was reported. The benzylic C(sp3)-H of tetrahydronaphthalene was activated through visible-light photoredox catalyst with oxygen as the clean oxidant under mild reaction conditions. This protocol proceeds efficiently with broad substrate scope, and the mechanism study was performed.

An Electrophilic Trifluoromethylthiolation of Silylenol Ethers and β-Naphthols with Diethylaminosulfur Trifluoride and (Trifluoromethyl)trimethylsilane

An efficient and general trifluoromethylthiolation of silylenol ethers and β-naphthols have been accomplished employing the combination of diethylaminosulfur trifluoride (DAST) and (trifluoromethyl)trimethylsilane (CF3TMS) as source of electrophilic trifluoromethylthio moiety for the synthesis of α-trifluoromethylthiolated carbonyl compounds and β-naphthols in good yields. Important features of this method include wide functional group tolerance and use of readily available DAST/CF3TMS. Potential of the methodology was demonstrated via the synthesis of α-trifluoromethylthiolated (+)-4-cholesten-3-one and naphthoquinone. (Figure presented.).

Revisiting secondary interactions in neighboring group participation, exemplified by reactivity changes of iminylium intermediates

Neighboring group participation is defined as the action of a substituent to stabilize a transition state or an intermediate by forming a bond or a partial bond with the reaction center. In addition to the primary interaction with the nearest neighboring group, secondary interactions involving another neighboring group(s) could also occur in principle. Here, we revisit this issue by examining the influence of secondary interactions on the stability and reactivity of the putative iminylium cation intermediates, formed by N-O bond cleavage of 1-tetralone oxime systems. A direct observation of a peri-bromo-iminylium intermediate in solution supported the involvement of iminylium cations and the stabilizing effect of secondary interactions arising from a distal tandem substituent. Both experimental and computational findings support the idea that secondary interactions of a tandem-neighboring group on the primary peri-heteroatom (Br, Cl, and O(Me))-iminylium bonding interaction, i.e., a weak halogen bonding interaction (ester (nitro) oxygen-halogen bonding) and an unprecedented hydrogen bonding interaction between a nitro oxygen atom and a CH3O hydrogen atom, are crucial determinants of the reaction pathway, leading to either overwhelmingly selective syn-migration of the oxime functionality or covalent bond formation under acid-catalyzed Beckmann rearrangement conditions.

Synthetic method of 7-bromo-3,4-dihydro-1(2H)-naphthalenone compound

The invention relates to a synthetic method of a 7-bromo-3,4-dihydro-1(2H)-naphthalenone compound. The method comprises the following steps: taking 4-(4-bromophenyl)butyric acid as a reactant and phosphorus pentoxide as dehydrating agent; mixing the reactant with the dehydrating agent; adding an organic solvent to carry out stirring and refluxing reaction; carrying out cooling reaction to a room temperature after the reaction is completed; separating out precipitants; carrying out suction filtration; purifying with acetone to obtain the 7-bromo-3,4-dihydro-1(2H)-naphthalenone compound. According to the synthetic method, by taking the phosphorus pentoxide as the dehydrating agent at first, the dehydrating agent of the 7-bromo-3,4-dihydro-1(2H)-naphthalenone compound is prepared, so that the product yield of the 7-bromo-3,4-dihydro-1(2H)-naphthalenone compound is greatly improved; moreover, the cost of the dehydrating agent is low, the using amount is little, the yield of the product after the completion of the reaction is up to 95 percent, and the purity of the product is high.

Highly enantioselective [3+2] coupling of cyclic enamides with quinone monoimines promoted by a chiral phosphoric acid

Enantioselective [3+2] coupling of cyclic enamides with quinone monoimines was realised using a chiral phosphoric acid as a catalyst. This transformation allowed for the synthesis of highly enantioenriched polycyclic 2,3-dihydrobenzofurans (up to 99.9% ee). The absolute configuration of one product was determined by an X-ray crystal structural analysis. We also found a possible mechanism for this reaction.

Sustainable flow oppenauer oxidation of secondary benzylic alcohols with a heterogeneous zirconia catalyst

A flow chemistry process for the Oppenauer oxidation of benzylic secondary alcohols using partially hydrated zirconium oxide and a simple carbonyl containing oxidant such as acetone, cyclohexanone, and neopentanal is reported. The heterogeneous oxidative system could be applied to a wide range of functionalized alcohol substrates, allowing clean and fast delivery of ketone products within a few minutes between 40 and 100 C.