[ CAS No. 942-01-8 ] {[proInfo.proName]}

Name: 942-01-8|2,3,4,9-Tetrahydro-1H-carbazole|98%
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SKU: A101605
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COA NMR CNMR HPLC LC-MS

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Product Details of [ 942-01-8 ]

CAS No. :	942-01-8	MDL No. :	MFCD00004959
Formula :	C₁₂H₁₃N	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	XKLNOVWDVMWTOB-UHFFFAOYSA-N
M.W :	171.24	Pubchem ID :	13664
Synonyms :

Calculated chemistry of [ 942-01-8 ]

Physicochemical Properties

Num. heavy atoms :	13
Num. arom. heavy atoms :	9
Fraction Csp3 :	0.33
Num. rotatable bonds :	0
Num. H-bond acceptors :	0.0
Num. H-bond donors :	1.0
Molar Refractivity :	55.73
TPSA :	15.79 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	Yes
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	Yes
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.02 cm/s

Lipophilicity

Log Po/w (iLOGP) :	2.09
Log Po/w (XLOGP3) :	3.28
Log Po/w (WLOGP) :	3.05
Log Po/w (MLOGP) :	2.76
Log Po/w (SILICOS-IT) :	3.98
Consensus Log Po/w :	3.03

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	2.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-3.48
Solubility :	0.0567 mg/ml ; 0.000331 mol/l
Class :	Soluble
Log S (Ali) :	-3.29
Solubility :	0.0885 mg/ml ; 0.000517 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-4.39
Solubility :	0.00702 mg/ml ; 0.000041 mol/l
Class :	Moderately soluble

Medicinal Chemistry

PAINS :	1.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.95

Safety of [ 942-01-8 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 942-01-8 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 942-01-8 ]
Downstream synthetic route of [ 942-01-8 ]

[ 942-01-8 ] Synthesis Path-Upstream 1~5

1
[ 942-01-8 ]
[ 16807-13-9 ]

Reference： [1] Organic and Biomolecular Chemistry, 2014, vol. 12, # 27, p. 4832 - 4836

2
[ 942-01-8 ]
[ 16807-13-9 ]
[ 86-74-8 ]

Reference： [1] Organic and Biomolecular Chemistry, 2014, vol. 12, # 27, p. 4832 - 4836

3
[ 942-01-8 ]
[ 3998-04-7 ]

Reference： [1] Organic and Biomolecular Chemistry, 2014, vol. 12, # 27, p. 4832 - 4836

4
[ 942-01-8 ]
[ 27387-31-1 ]

Reference： [1] Journal of Chemical Crystallography, 1995, vol. 25, # 5, p. 249 - 258
[2] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 12, p. 1606 - 1610

5
[ 56-23-5 ]
[ 942-01-8 ]
[ 2805-84-7 ]

Reference： [1] Tetrahedron Letters, 2004, vol. 45, # 1, p. 21 - 23

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Yield	Reaction Conditions	Operation in experiment
99%	With sodium periodate In methanol
84%	With urea hydrogen peroxide adduct at 45℃; for 24h;
63%	With Oxone; sodium hydrogencarbonate In water; acetone at 20℃;	General procedure for the oxidation reactions using dimethyldioxirane generated in situ General procedure: Reactions were generally conducted on a scale of1 to 10 mmol of the indolic substrate. The followingprocedure is representative. The substrate (10 mmol) wassolubilized in aqueous acetone (50:45 mL) to which wasadded NaHCO3 (3.4 equiv., 34 mmol). Subsequently,Oxone (10 mmol) was added in portions during a periodof 10 min at room temperature. CO2 evolution was noted.After 30-60 min, TLC analysis of the reaction revealedthe complete consumption of the respective substrate andthe formation of the products. The reaction was dilutedwith aqueous NaCl solution (10%, 70 mL) and extractedwith CH2Cl2 (4 × 50 mL). The organic phase was driedwith Na2SO4, filtered and concentrated under reducedpressure to give the crude product as an oil, which solidifiedwith time. The crude products were Na-deacetylated(see “Na-Deacetylation of the oxidatively rearrangeddiastereoisomeric mixtures” section) unless otherwisestated. The substrates, methyl N-acetyltryptophan ester (5)and tetrahydrocarbazol (6), gave products resulting fromoxidative cleavage of the indolic double bond (8 and 9,respectively). DMD oxidation of the substrate 7 gave theoxindole 10 in 83-92% yield, Na-deacetylated product wasnot quantified.81 The crude products were purified using aChromatotron (eluent: hexane:EtOAc, 3:1).

	With ozone; ethyl acetate unter Kuehlung;
	With oxygen; ethyl acetate; platinum anschliessendes Erwaermen;
	With methanol; ozone unter Kuehlung;
	Multi-step reaction with 2 steps 1: diethyl ether; hydrogen peroxide 2: chloroform

Yield	Reaction Conditions	Operation in experiment
100%	With oxygen; rose bengal In toluene at 20℃; for 3h; Irradiation;
90%	With oxygen; rose bengal In toluene for 24h; Irradiation;
90%	With oxygen; rose bengal; acetic acid Irradiation;

Yield	Reaction Conditions	Operation in experiment
80%	With sodium nitrate; sulfuric acid In water for 1.5h;	General procedure for the nitration oftetrahydrocarbazole, 2 To a solution of sodium nitrate (1.70 g, 0.0200M )in concentrated sulphuric acid (50 mL) (H2SO4), wasadded drop wise with stirring, over a period of 1h, asolution of 2,3,4,9-tetrahdrocarbazole (3.18g, 0.0200M) in 25 mL of concentrated sulphuric acid (H2SO4) and keep at 5°C in an ice bath. The solution wasstirred for an additional 5 min and then poured ontocrushed ice. The crude product was recrystallizedfrom methylene chloride-petroleum ether (1:1). Theorange yellowish blunt needles of the pure 6-nitro-2,3,4,9-tetrahydrocarbazole 2 were obtained ascrystals.
	With sulfuric acid; potassium nitrate at -5 - -3℃;

[ CAS No. 942-01-8 ] {[proInfo.proName]}

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Product Details of [ 942-01-8 ]

Calculated chemistry of [ 942-01-8 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 942-01-8 ]

Application In Synthesis of [ 942-01-8 ]

[ 942-01-8 ] Synthesis Path-Upstream 1~5

[ 942-01-8 ] Synthesis Path-Downstream 1~88

Precautionary Statements-General

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	With oxygen; ethyl acetate; platinum
	With oxygen In toluene at 15 - 25℃; for 3h; Photolysis;	1 For the second embodiment, the product with the product number as indicated in the following table and having the general formula (V) was obtained by "coupling in two steps": In the first step, the substrate (I) is transformed to intermediate (III) by the action of singlet oxygen, for example, by reacting (I) with oxygen in the presence of a sensitizer like rose bengal or tetraphenylporphyrine under irradiation by a lamp or sunlight in a solvent such as toluene at room temperature in the range of 15° to 25°C. The intermediate can be directly employed in the second step without purification. A change of solvent to methanol or acetic acid is usually necessary if the oxidation step is performed in another solvent. In the second step, the intermediate (III) is transformed to the product (IV) by reacting with a nucleophile in the presence of a Lewis or Br0nsted acid. The inventors have found that two separate catalysts, one photocatalyst and one acid catalyst, give the best results in the second embodiment ("two-step coupling").

Yield	Reaction Conditions	Operation in experiment
96%	With copper(II) choride dihydrate In dimethyl sulfoxide at 100℃; for 7h;	General procedure for the synthesis of compounds (2a-2q), (7a-7d), (9, 11, 13) General procedure: A mixture of starting compound (2.69 mmol), CuCl2.2H2O (10 mol %) in DMSO (5 mL) stirred at 100 °C. The reaction progress was monitored by thin layer chromatography (PMA was used for stain solution). The reaction mixture was poured into ice cold water. The crude product was purified by column chromatography using ethyl acetate and petroleum ether as eluent to afford carbazoles.
92%	With ethene; palladium 10% on activated carbon In acetonitrile at 100℃; for 96h; Sealed tube;
83%	With vanadium(V) oxide; acetic acid at 118℃; for 24h; Inert atmosphere;

81%	With zircon sand In sulfolane at 280℃;	4.2 preparation of carbazole In the reaction flask, 30 g of tetrahydrocarbazole, 1000 g of sulfolane, 60 g of catalyst zircon sand were added, and the mixture was heated to 280°C to reflux reaction, HPLC control reaction end, filter recovery catalyst, filtrate distillation recovery sulfolane, cooling crystallization, filtration washing, drying carbazole, yield 81%.
75%	With palladium on activated charcoal In 1,3,5-trimethyl-benzene for 2h; Heating;
63%	With chloranil In xylene for 24h; Heating;
55%	With palladium on activated carbon In 1,3,5-trimethyl-benzene at 150℃; for 24h; Inert atmosphere;
	With lead oxide pumice stone durch Destillation;
	With hydrogen at 400℃; beim Leiten ueber einen Kupferoxid-Chromoxid-Bariumoxid-Katalysator;
	With nickel; xylene
	With benzene at 300℃; beim Erhitzen an einem Nickel-Nickeloxid-Chromoxid-Katalysator;
	With palladium on activated charcoal; trimethylbenzene
	With palladium; Cinnamic acid at 200℃;
	With chloranil; xylene
	With diphenyl sulfide at 270℃;
	With palladium on activated charcoal; xylene
	In various solvent(s) for 7h; Heating;
	With molybdenum carbide In 1,3,5-trimethyl-benzene at 149.84℃; Inert atmosphere;
	Stage #1: 1,2,3,4-tetrahydrocarbazole With magnesium sulfate heptahydrate In dichloromethane Stage #2: With palladium 10% on activated carbon at 120℃; for 0.0333333h; Microwave irradiation;
	With iodine In dimethyl sulfoxide at 100℃; for 10h;
	With propene In 1,3,5-trimethyl-benzene at 150℃; Inert atmosphere; Flow reactor;

Yield	Reaction Conditions	Operation in experiment
86%	With platinum/carbon xerogel catalyst; hydrogen; toluene-4-sulfonic acid In water at 25℃; for 3h; regioselective reaction;
80%	With bis(trifluoroacetoxy)borane-tetrahydrofuran In tetrahydrofuran; trifluoroacetic acid
78%	With sodium cyanoborohydride In acetic acid at 20℃; for 12h;

78%	With sodium cyanoborohydride; acetic acid at 20℃; for 0.5h;
75%	With hydrogenchloride; tin In ethanol; water at 70℃; for 4h; Inert atmosphere;
63%	With perchloric acid; palladium 10% on activated carbon; hydrogen In acetic acid at 20℃; for 24h;
30%	With zinc borohydride In diethyl ether for 48h; Ambient temperature;
	With hydrogenchloride; tin
	With phosphorus; hydrogen iodide
	With sulfuric acid at 60℃; Electrolysis;
	With sulfuric acid Electrolysis;
	With sodium cyanoborohydride; acetic acid Ambient temperature; Yield given;
	With trimethylamine-borane

Yield	Reaction Conditions	Operation in experiment
99%	With potassium hydrogensulfate; silica gel for 0.0138333h; microwave irradiation;
98%	With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide In ethyl acetate at 100℃; for 0.0833333h; Microwave irradiation; Sealed vessel;	1. Typical procedure for a T3P mediated Fischer indole synthesis General procedure: T3P (50% in EtOAc) (0.55-0.68 mmol) was added to a mixture of hydrazine (59 mg, 0.55 mmol) and ketone/aldehyde (0.55 mmol) in a microwave vial. The reaction volume was then made up to 0.5 mL with EtOAc and the vessel was sealed under air. The mixture was heated under microwave irradiation (Biotage Initiator) at 100-150 °C for 5-15 min. The solvent was evaporated under reduced pressure and the oily residue was purified by filtration through a plug of silica gel (eluent: isohexane/EtOAc, 8:2) to yield the desired indole or tetrahydrocarbazole. When the reaction was conducted on a 5 mmol scale the product (3a) was purified by precipitation from acetone/water.
97%	With acetic acid In isopropyl alcohol at 200℃; Continuous-flow;

94%	With trichloroacetic acid at 100℃; for 0.0833333h;
93%	With 1,3-bis(3-sulfopropyl)-1H-imidazol-3-ium hydrogensulfate In water at 80℃; for 0.5h;
92%	With aluminium trichloride; n-butylpyridinium chloride for 0.583333h; Heating;
92%	With liquid 1-butyl-3-methylimidazolium hydrosulfate at 70℃; for 1h;
91%	With acetic acid at 150℃; microwave irradiation;
91%	With toluene-4-sulfonic acid for 0.05h; Microwave irradiation; neat (no solvent);
91%	With acetic acid for 0.25h; Reflux;	General Procedure for Synthesis of Substituted2,3,4,9-tetrahydro-1H-carbazoles (3-6) General procedure: The amalgamation of tetrahydrocarbazoles were based on Fischer-indole synthesis method. In general it was carried out by dissolving 8.8 g (0.08 mol) of cyclohexanone in 50 ml of glacial acetic acid, to this 8.8 g (0.08 mol) of substituted phenyl hydrazine was added and boiled under reflux for 15 min. the solution was cooled, crystals formed were isolated by filtration. Crude product was further purified by recrystallization from aqueous ethanol. A total of four derivatives were synthesized by this route and were subjected to characterization. 2,3,4,9-Tetrahydro-1H-carbazole (3) Yield 91 %; mp 117 - 119 C (ethanol); Rf 0.39 (n - Hexane:EtoAC,7:3); IR (KBr) cm-1: (N-H stretching) 3314.12,(C-H Stretching aliphatic) 2954.8, (C=C Stretching) 1623,(C-N stretching) 1513; 1H NMR (CDCl3, 400 MHz): 2.08 (m,2H, ABq, CH2), 2.20 (m, 2H, ABq, CH2), 2.28 (m,4H,CH2),3.90 (s, 1H, NH), 6.73 (m, 4H, Ar); 13C NMR: 115.76,118.50, 129 (Ar), 168.16, 169.10, 170.12 (Tetrahydrocarbazole);Em (Es, Positive mode) m/, 1171.165; Anal. Calcd %for (C12H13N); C,84.59; H,9.68; N,5.80; Found: C,84.59;H,9.69; N,5.81.
90%	In ethylene glycol thermal reaction;
90%	In propan-1-ol; acetic acid at 210 - 230℃; Microwave irradiation; Continuous-flow;
90%	With sulfonic acid functionalized mesoporous silica SBA-15-Pr-SO₃H In ethanol for 1.33333h; Reflux; Green chemistry;
89%	With acetic acid for 8.5h; Reflux;
88%	With acetic acid for 0.0833333h; Reflux;	General procedure for the synthesis oftetrahydrocarbazole Refluxing of phenylhydrazine and cyclohexanonein glacial acetic acid for 5 min, leads the conversionof cyclohexanone into phenylhydrazone, without itsisolation, (Scheme I) being converted into 2,3,4,9-tetrahydrocarbazole. The solid was filtered in vacuoand recrystallized with ethanol instantly.
85%	With Amberlite IR 120 In ethanol at 80℃; for 12h;	EXPERIMENTAL General procedure: A mixture of the carbonyl compound (5, 1.0 mmol), arylhydrazine (6, 1.2 mmol), and the solid acid (7, Amberlite, 1.5 g, obtained from Aldrich Chemical Co.) was refluxed in absolute ethanol (10 ml) for 8 h. The reaction was monitored by thin-layer chromatography(TLC), and upon completion the mixture was cooled to room temperature, the catalyst filtered off, and the product was washed thoroughly with ethylacetate (30 ml). The combined organics were washed with water, dried (Na2SO4), and concentrated in vacuo. The resulting residue was chromatographed on a silicagel column eluting with ethylacetate-hexane mixtures to obtain the purified indole (8). This was fully characterized by infrared, 400-MHz 1H NMR, high-resolution mass spectrometry, and melting point (solids).
83.4%	With molecular sieve for 0.05h; microwave irradiation;
82%	With choline chloride; zinc(II) chloride at 95℃; for 4h;
77%	With sulfuric acid In water for 1h; Reflux;	2.1 (1) Preparation of Compound 8 In a 50mL three-necked flask,Add phenylhydrazine 2.26g (20.4mmol),Cyclohexanone 1.72g (20.4mmol),10mL tap water,After stirring evenly,1.4 mL of concentrated sulfuric acid was added dropwise at room temperature.After the addition is completed,Reflux 1h,Cool to room temperature,Pour off the supernatant.Add 50 mL of n-hexane to the three-necked flask.Warming and refluxing for 30 min,Pour the supernatant after a little cold,Place the refrigerator to freeze,A white solid precipitated.Repeat the above operation 3-5 times,Filtered to a white solid of 2.69 g.The yield was 77%.
75%	With phosphorus trichloride In benzene for 0.5h; Ambient temperature;
75%	With acetic acid In acetonitrile for 1.08333h; Flow reactor; Microwave irradiation;
70%	With acetic acid for 1h; Reflux;	4.1.1 4.1.1. Synthesis of 2,3,4,9-tetrahydro-1H-carbazole (1) Synthesis of 2,3,4,9-tetrahydro-1H-carbazol (1) was prepared according to the published procedure [25]. To a mixture of cyclohexanone (10 mmol), acetic acid (60 mmol) and phenyl hydrazine (10 mmol) were added and reflux for 1 h. The progress of reaction was check by TLC. The mixture was kept in room temperature overnight and then white solid crude was filtered and washed with water and ethanol (75%) respectively. The solid material was crystalized in methanol to yield compound 1.
67%	In acetic acid for 1h; Heating;
65%	1) 5 min 2) 5 min, 120 deg C;
62%	With soluble asphaltene oxide In water at 150℃; for 1.5h;
53%	With hydrogenchloride; acetic acid at 120℃; for 2h;
	With acetic acid
	With acetic acid at 60℃; Yield given;
	Stage #1: cyclohexanone; phenylhydrazine In para-xylene at 140℃; Inert atmosphere; Stage #2: With hydrous zirconia-supported niobium oxide In para-xylene at 140℃; Inert atmosphere;
	With amberlite IR 120H In ethanol at 70℃; for 0.0578333h; flow reactor;
	With hydrogenchloride In water at 50 - 60℃; for 5h;	General procedure: Substituted phenyl hydrazine (14 mmol) was solved in the mixture of concentrated hydrochloric acid and water (50 mL, 1:20) and then ketone (16.8 mmol) was added dropwise at rt. After that, the mixture was stirred for more than 5 h at 50-60 . When the reaction cooled to rt, some rice shape solids appeared in the system. The mixture was filtered and the solid was washed with enough water until neutral.T he crude product was recrystallized in hexane to afford 1k-1q in 72-95% yield.
	With hydrogenchloride; L-Tartaric acid; 1,3-bis(hydroxymethyl)urea In water at 70℃;
	In neat (no solvent, gas phase)

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: 1,2,3,4-tetrahydrocarbazole With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 1h; Inert atmosphere; Schlenk technique; Glovebox; Stage #2: methyl iodide In tetrahydrofuran; mineral oil at 0 - 20℃; for 1h; Inert atmosphere; Schlenk technique; Glovebox;
93%	Stage #1: 1,2,3,4-tetrahydrocarbazole With sodium hydride In tetrahydrofuran at 20℃; for 1h; Stage #2: methyl iodide In tetrahydrofuran at 20℃; for 0.25h; Further stages.;
90%	With ammonia; sodium In diethyl ether

30%	With sodium hydride In tetrahydrofuran; mineral oil at 20℃;	General Procedure A: N-methylation of Indole Derivatives General procedure: In a flame-dried flask, the indole (1.0 eq) was dissolved in THF (10 mL). Sodium hydride (60% w/w, 1.5 eq) was added in one portion, then methyl iodide (2.0 eq) was added dropwise. The reaction was stirred at rt until consumption of starting material was observed by TLC. The reaction was diluted with ethyl acetate (10 mL) and the excess NaH was quenched with water (15 mL). The organic layer was separated, and the aqueous layer was extracted with ethyl acetate (3 x 10 mL). The combined organic layers were washed with brine (15 mL), dried over MgSO4, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography.
	With potassium hydride In tetrahydrofuran
	Stage #1: 1,2,3,4-tetrahydrocarbazole With sodium hydride In tetrahydrofuran at 80℃; for 2h; Stage #2: methyl iodide In tetrahydrofuran at 80℃; for 1h;
	Stage #1: 1,2,3,4-tetrahydrocarbazole With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran; mineral oil at 0 - 20℃; for 1.08333h; Schlenk technique; Inert atmosphere;
	Stage #1: 1,2,3,4-tetrahydrocarbazole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide; mineral oil at 0 - 20℃;
108 mg	Stage #1: 1,2,3,4-tetrahydrocarbazole With sodium hydride In tetrahydrofuran; N,N-dimethyl-formamide; mineral oil at 80℃; for 0.0833333h; Microwave irradiation; Stage #2: methyl iodide In tetrahydrofuran; N,N-dimethyl-formamide; mineral oil at 80℃; for 0.5h; Microwave irradiation; regioselective reaction;

Yield	Reaction Conditions	Operation in experiment
80%	With orthoperiodic acid In tetrahydrofuran; lithium hydroxide monohydrate at 0℃;
75%	With periodic acid In methanol at -10 - 20℃;	1 Synthesis of Intermediate M-2: In a 250 ml flask, 0.01 mol of periodic acid and 2 ml of methanol were stirred at room temperature for 30 minutes. The reaction solution was cooled to -10°C, and then 0.01 mol of intermediate M-1 methanol solution (5 mL) was slowly added dropwise to the reaction mixture. After the dropwise addition was completed, the reaction solution was naturally raised to room temperature. The reaction solution was poured into ice water, the product was extracted with ethyl acetate, the organic phase was separated, and the organic phase was washed with sodium thiosulfate solution, then dried over anhydrous sodium sulfate, and white solid M-2 (yield) was passed through column chromatography. 75%).
71%	With periodic acid In methanol at -10 - 20℃;	4 Periodic acid (4.95 mg, 21 mmol) and 2 ml of methanol were stirred at room temperature for 30 minutes in a 250 ml round bottom flask.The reaction flask was cooled to -10 ° C and then a solution of intermediate M4-1 (3.72 mg, 21 mmol) in methanol (6 mL) was slowly added dropwiseTo the reaction mixture (cautious control of the reaction liquid temperature does not increase), the dropwise addition is completed, the reaction solution was slowly raised from low to room temperature.The progress of the reaction was monitored by TLC until the oxidation reaction was complete.The reaction solution was poured into ice-water and the product was extracted with ethyl acetate. The organic phase was separated and the organic phase was washed with sodium thiosulfate solution and then dried over anhydrous sodium sulfate. The product was separated and purified by column chromatography acetate: 9.5: 0.5) to give 2.75 g of M4-2 as a white solid in 71% yield.

65%	With diiodine pentaoxide In tetrahydrofuran; lithium hydroxide monohydrate at 20℃; for 0.333333h;	To a stirred solution of commercially available 1,2,3,4-tetrahydrocarbazole (5.00 g,29.2 mmol, 1.0 eq) in 300 mL THF and 75 mL water was added diiodine pentoxide(11.7 g, 35.1 mmol, 1.2 eq). After stirring for 20 min at room temperature, the solvent was removed in vacuo at room temperature. The residue was extracted with ethylacetate. The organic portion was washed with water, 5% Na2S2O3, saturated sodium bicarbonate and brine, and dried over MgSO4. After removing the solvent, the crude product was purified by recrystalisation (EtOAc/hexanes, 1/19) to afford title compound as white solid (3.5 g, 18.98 mmol, 65%);
65%	With orthoperiodic acid In methanol; lithium hydroxide monohydrate at -15 - 20℃; for 18h; Inert atmosphere;
55%	With diiodine pentaoxide In tetrahydrofuran; lithium hydroxide monohydrate at 20℃; for 0.333333h;
53%	With diiodine pentaoxide In tetrahydrofuran; lithium hydroxide monohydrate Ambient temperature;
52%	With diiodine pentaoxide In tetrahydrofuran; lithium hydroxide monohydrate at 0 - 20℃; for 1h;	Reactant: 1,2,3,4-Tetrahydrocarbazole (119). 119 (5.0 g, 29.20 mmol) was dissolved in 80% (v/v)aqueous THF (100 mL). The mixture was cooled to 0 °C before I2O5 (11.70 g, 35.04 mmol) was addedin portions. After stirring for 1 h at RT solvent was evaporated and the residue extracted with 100 mLethyl acetate. The extract was successively washed with water, 5 % Na2S2O3 solution, saturatedNaHCO3 and brine. The organic phase was dried, concentrated and purified by columnchromatography (chloroform-methanol, 90:10 (v/v) and n-hexane-ethyl acetate, 60:1 (v/v)). Unsoiledfractions were crystallized from methanol to give light yellow crystals: 123 (2.80 g, 52 %).
	With orthoperiodic acid at -10 - 20℃; for 18h; regioselective reaction;

Yield	Reaction Conditions	Operation in experiment
85%	With hydrogenchloride; tin In ethanol; water at 20 - 90℃; for 4h; Inert atmosphere;
78%	With palladium 10% on activated carbon; hydrogen In tetrahydrofuran at 20℃; for 12h;	2.2 (2) Preparation of Compound 9 8 3.55g (20.7mmol),10% Pd/C 0.70g,Add 70mL of tetrahydrofuran,Hydrogen gas is introduced into the reaction solution at room temperature using a hydrogen balloon.After 12 hours of reaction,Filtering,Recycling Pd/C,The filtrate is dried,Column chromatography (neutral alumina, PE: EA = 100:1) gave a pale yellow oil of 2.80 g.The yield was 78%.
57%	With tetrabutylammonium borohydride In dichloromethane for 10h; Heating;

Yield	Reaction Conditions	Operation in experiment
53%	With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; methanesulfonic acid at 170℃; for 48h; Inert atmosphere;
48%	With toluene-4-sulfonic acid In neat (no solvent) at 175℃; for 48h;	General procedure for indole synthesis of aniline by diols catalyzed by nickel supported on silica General procedure: Diol (10.9 mmol, 1 equiv.), 65 wt% Ni/SiO2-Al2O3 (198 mg, 0.2 equiv.), aniline (21.9 mmol, 2equiv.) and PTSA (209 mg, 0.1 equiv.) were introduced in that order in a 50 mL round bottom flask, which was then equipped with an open condenser. The mixture was stirred at 175 °C for 48 h. After this duration, a sample of the crude mixture was diluted in ethyl acetate, filtered and analyzed by GC. 2-3 g of silica was added to the crude mixture, which was then concentrated under reduced pressure and purified by flash chromatography (ethylacetate/cyclohexane : 5 : 95) to afford the desired product.
46%	In 1,4-dioxane at 180℃; for 50h;

Yield	Reaction Conditions	Operation in experiment
96.7%	With tetrapropylammonium iodide; potassium hydroxide at 20℃;	General procedure for synthesis of epoxides E2 to E10 General procedure: To the corresponding indole or phenol (1 eq) dissolved in epichlorohydrin (1.4 ml/mmol) powdered potassium hydroxide (400 mol %) and tetrapropylammonium iodide (10 mol %) was added and the mixture was stirred at room temperature for 1-4 hr. Upon completion the reaction mixture was extracted (3X) with dichloromethane and washed with a solution of 1:1 brine and water and the combine organic layers were concentrated. Further purification was accomplished using silica column chromatography with 5-10% ethyl acetate in hexanes to give the corresponding epoxide.
81%	Stage #1: 1,2,3,4-tetrahydrocarbazole With sodium hydride In N,N-dimethyl-formamide at 0 - 25℃; Inert atmosphere; Stage #2: epichlorohydrin In N,N-dimethyl-formamide at 0 - 25℃; Inert atmosphere; Stage #3: With water In N,N-dimethyl-formamide	6.1.4. General procedure for the synthesis of GJP14 and its derivatives 1-5. A representative procedure for the synthesis of 1-(1-piperidinyl)-3-(1,2,3,4-tetrahydro-9H-carbazol-9-yl)-2-propanol (2d) A solution of 2,3,4,9-tetrahydro-1H-carbazole (3a, 171 mg, 1.00 mmol) in DMF (1 mL) was added to a suspension of sodium hydride (26 mg, 1.1 mmol) in DMF (4 mL) at 0 °C, and the mixture was stirred at 25 °C for 1 h. Epichlorohydrin (102 mg, 1.10 mmol) was added to the resulting solution at 0 °C, and the mixture was stirred at 25 °C for 12 h. The reaction mixture was poured into water and extracted with CH2Cl2. The organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by MPLC on a silica gel using hexane/CHCl3 as the eluent and GPC using CHCl3 as the eluent to produce 1-(2,3-epoxypropyl)-2,3,4,9-tetrahydro-1H-carbazole (2d', 185 mg, 0.814 mmol, 81% yield) as a pale yellow oil. 1H NMR (CDCl3): δ 1.84-1.96 (m, 4H), 2.46 (dd, J = 2.6, 4.9 Hz, 1H), 2.71-2.76 (m, 5H), 3.19-3.22 (m, 1H), 4.14 (dd, J = 4.8, 15.7 Hz, 1H), 4.30 (dd, J = 3.6, 15.7 Hz, 1H), 7.08 (dt, J = 0.9, 7.6 Hz, 1H), 7.08 (dt, J = 1.1, 7.6 Hz, 1H), 7.29 (d, J = 7.6 Hz, 1H), 7.47 (d, J = 7.7 Hz, 1H). 13C NMR (CDCl3): δ 21.0, 22.2, 23.1, 23.3, 44.2, 45.5, 51.0, 108.6, 110.0, 117.9, 119.0, 120.9, 127.5, 135.6, 136.6. IR (ATR): 1256 cm-1. MS (EI): m/z 227 (M+). HRMS calcd for C15H17NO: 227.1310. Found: 227.1323. Piperidine (104 mg, 1.22 mmol) was added to a solution of 2d' (185 mg, 0.814 mmol) in EtOH (5 mL) at 25 °C, and the mixture was stirred under reflux for 12 h. After the solvent was evaporated, the residue was purified by MPLC on a silica gel using CHCl3/MeOH as the eluent to give 2d (221 mg, 0.707 mmol, 87% yield) as a colorless solid.
56%	With potassium hydroxide In dimethyl sulfoxide for 2h; Ambient temperature;

Yield	Reaction Conditions	Operation in experiment
49%	Stage #1: 1,2,3,4-tetrahydrocarbazole With potassium hydroxide In dimethyl sulfoxide at 25℃; for 1h; Inert atmosphere; Stage #2: 2-bromoethanol In dimethyl sulfoxide at 0 - 25℃; Inert atmosphere;	Synthesis of 2-(1,2,3,4-Tetrahydro-9H-carbazol-9-yl)ethanol (3c). Compound 3a (171 mg, 1.00 mmol) was added to a suspension of KOH (224 mg, approximately 4 mmol) in DMSO (2 mL) at 25 °C, and the mixture was stirred at that temperature for 1 h. 2-Bromoethanol (137 mg, 1.10 mmol) was added to the mixture at 0 °C, and the mixture was stirred at 25 °C for 12 h. The reaction mixture was poured into water and extracted with CH2Cl2 (10 mL). The organic layer was washed with water (10 mL ' 3), dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by MPLC on a silica gel using CHCl3/MeOH as the eluent to produce compound 3c (106 mg, 0.492 mmol, 49% yield) as a colorless oil. 1H NMR (CDCl3): d 1.72-1.94 (m, 4H), 2.70 (t, J = 5.9 Hz, 4H), 3.79 (t, J = 5.5 Hz, 2H), 4.10 (t, J = 5.5 Hz, 2H), 7.06 (dt, J = 0.9, 7.7 Hz, 1H), 7.12 (dt, J = 1.1, 7.7 Hz, 1H), 7.25 (d, J = 7.7 Hz, 1H), 7.44 (d, J = 7.7 Hz, 1H). 13C NMR (CDCl3): d 21.1, 22.3, 23.2, 23.3, 45.1, 61.9, 108.8, 109.7, 117.9, 118.9, 120.8, 127.5, 135.7, 136.4. IR (ATR): 3353 cm-1. MS (EI): m/z 215 (M+). HRMS calcd for C14H17NO: 215.1310. Found: 215.1313. RT (GC/MS): 10.8 min (method B). PrPres level (10 mM): 90 +/- 7%.
	With sodium hydroxide In dimethyl sulfoxide

Yield	Reaction Conditions	Operation in experiment
91%	With dimethyl(phenyl)silyl lithium In tetrahydrofuran for 3h;
80%	With lithium hydroxide; mercaptoacetic acid In N,N-dimethyl-formamide at 20℃; for 3h;
80%	With mercaptoacetic acid; lithium hydroxide In N,N-dimethyl-formamide at 20℃; Inert atmosphere;	4.1.27. Detosylation of N-tosyl-indoles and -imidazoles-general procedure General procedure: The N-tosyl indole or imidazole 66 (0.50 mmol) was dissolved in DMF (2 mL). Lithium hydroxide (48 mg, 2.00 mmol) was added followed by thioglycolic acid (30 mL, 0.60 mmol). The resulting solution was stirred at ambient temperature and the reaction progress monitored by TLC. Once reaction was complete (1.5-5 h), the solution was diluted with ethyl acetate (4 mL) and water (2 mL) and the layers separated. The aqueous layer was extracted with ethyl acetate (2×4 mL) and the combined organic solutions washed with saturated aqueous sodium carbonate (3×5 mL) then dried, filtered and evaporated to leave an essentially pure N-H indole or imidazole 67. Each product was identified by comparisons of mp and 1H NMR data with authentic material.

Yield	Reaction Conditions	Operation in experiment
99%	With glacial acetic acid at 90 - 120℃; for 1h;	1.1 preparation of tetrahydrocarbazole In a 1 L round bottom flask was charged with cyclohexanone (1 mol), 80% acetic acid (400 mL) was add and controlled temperature of 90 °C. 6 batches of phenylhydrazine hydrochloride (1 mol) were added and the reaction was stirred at 120 ° C for 1 hour. HPLC reaction, filtration, filtrate recovery, filter cake washed with water and 60% ethanol washing, drying to get tetrahydrocarbazole, the yield of 99%.
97%	With L-(+)-tartaric acid-urea melt at 70℃; for 0.25h;
96%	With 1-(3-sulfopropyl)pyridinium p-toluenesulfonate In lithium hydroxide monohydrate at 100℃; for 0.166667h;	5 Example 5 Sulfonic acid ionic liquid 1b (0.125 mmol), phenylhydrazine hydrochloride (25 mmol),Cyclohexanone (25 mmol) water 15 mL sequentially added to the reaction vessel,Placed in a reactor, under mechanical stirring, 100 ° C for 10 minutes,Cooled to room temperature, the mixture was filtered, dried 4.11 g, yield 96%.

96%	With 1,3-bis(3-sulfopropyl)-1H-imidazol-3-ium trifluoromethanesulfonate In lithium hydroxide monohydrate at 100℃; for 0.25h; Microwave irradiation; Green chemistry;	3 4.3 Representative procedure for the one-pot Fischer indole synthesis General procedure: Cyclohexanone (0.91 g, 10.0 mmol) was mixed with [(HSO3- p)2im][CF3SO3] (0.5 mmol) in water (15 mL), and phenylhydrazine hydrochloride (1.44 g, 10.0 mmol) was added. The mixture was then stirred at 100 8C for about 15 min under microwave irradiation. Reaction progress was monitored by GC-MS. After completion, the reaction mixture was cooled to room temperature, and 1,2,3,4-tetrahydrocarbazole was obtained by filtration. The remaining mixture of [(HSO3-p)2im][CF3SO3]/H2O was reused directly. 1H NMR (500 MHz, CDCl3, d ppm): 1.86-1.93 (m, 4H), 2.70-2.74 (m, 4H), 7.05-7.12 (m, 2H), 7.27-7.29 (d, 1H, J = 7.5 Hz), 7.45-7.47 (d, 1H, J = 7.5 Hz), 7.67 (s, 1H). (Experimental procedures, spectra and NMR data for the complexes see supporting information)
95%	With ammonium cerium (IV) nitrate In methanol for 2h; Reflux;
95%	With antimony(III) sulfate In methanol for 0.666667h; Reflux;
95%	With Bi(NO₃)₃·5H₂O In methanol for 0.666667h; Reflux;
94%	With 4-methylbenzenesulfonic acid-based ionic liquid supported on silica gel In ethanol at 20℃; for 4h;	2.3 General Procedure for the Synthesis of Indoles General procedure: To a solution of phenylhydrazine (10 mmol) and ketone or aldehyde (10 mmol) in ethanol (15 mL) was added catalyst IL-SO3H-SiO2 (1.2 g). The mixture was allowed to stirringat room temperature for a period time specified in Table 2.The reaction was monitored by TLC and GC. After completionof the reaction, the catalyst was recovered by filtration.Evaporation of the solvent under reduced pressuregave the crude product. Further purification was achievedby flash column chromatography on a silica gel to give thedesired product. The recovered catalyst was dried andreused for the next run. Spectroscopic data for selectedproducts is as follows.
94%	With HZSM-5-supported Brönsted and Lewis acidic ionic solid 1,3-disulfoimidazolium chlorozincate material ([dsim]₂[ZnCl₄](at)HZSM-5=17%) In neat (no solvent) at 100℃; for 0.75h;
92%	With glacial acetic acid for 8h; Reflux;	General procedure for the synthesis of starting substrate tetrahydrocarbazoles (1a-1q, 1v) General procedure: A substituted phenyl hydrazine. HCl (4.61 mmol) was added to the mixture of cyclohexanone (4.61 mmol) and acetic acid (15 ml) portion wise for 30 min. The mixture was then refluxed for 8 h and progress of reaction was monitored by thin layer chromatography. The reaction mixture was cooled and poured into crushed ice. The solid product was separated, filtered, dried and recrystallized from the methanol solvent.
90%	In glacial acetic acid for 0.00777778h; microwave irradiation;
90%	In glacial acetic acid for 0.00777778h; microwave irradiation;
89%	With 4-(dimethylamino)-1-pentylpyridin-1-ium fluoride; anhydrous zinc chloride In ethanol at 78 - 80℃; Inert atmosphere;	7; 8 Procedure for Substituted Tetrahydro-1H-carbazole (Indoles)/Methyl Tetrahydro-1H-carbazole (Indolenines) Synthesis General procedure: In a general procedure, an oven dried round bottomed flask was charged with corresponding phenyl hydrazine hydrochloride (1 mmol, 1 equiv.) and ethanol (3 mL). To the resulting solution corresponding 43uinolone43one/methyl cyclohxanone (1 mmol, 1 equiv.) and 4-(dimethylamino)-1-pentylpyridin-1-ium fluoride (2) [or (II)] (0.2 mmol, 0.2 equiv.) was added at room temperature and mixture was heated at reflux (78-80° C.) under nitrogen atmosphere. The consumption of starting material was monitored by thin layered chromatography by using eluents ethyl acetate/hexane (3:7). The crude reaction mixture was directly purified by silica gel column chromatography by using eluents in gradient eluents EtOAc/Hexane (1:9 to 1:1) to get the corresponding pure products (6a-h) in different yields.
88%	Stage #1: N-phenylhydrazine monohydrochloride With sodium hydroxide In lithium hydroxide monohydrate at 70℃; for 0.5h; Stage #2: cyclohexanone In glacial acetic acid Reflux;
86%	With ammonium cerium (IV) nitrate In methanol for 4h; Reflux;
85%	With glacial acetic acid for 8.5h; Reflux;	4 Phenylhydrazine hydrochloride (1.44 g, 10 mmol) was added portionwise to a solution of cyclohexanone (1.00 g, 10 mmol) in 30 ml of acetic acid over 30 minutes in a 100 ml three-necked flask and refluxed for 8 hours. The reaction was complete.The reaction was also cooled to room temperature and then poured into ice-water. The solid was collected by filtration and recrystallized from methanol to give Intermediate M4-1 as a white solid, 1.44 g, in 85% yield.
85%	With hydrogenchloride; 9-mesityl-10-phenylacridin-10-ium tetrafluoroborate; oxygen In lithium hydroxide monohydrate; acetonitrile at 20℃; for 24h; Irradiation; Sealed tube;
80%	With N,N′-dimethylurea; tartaric acid at 80℃; Inert atmosphere;
80%	With mesoporous silica at 20℃; for 3h; Milling;	General Procedure: Mechanochemical Fischer Indolisation General procedure: The phenylhydrazine salt, cyclohexanone and silica were added to a stainless-steel jar (12 mL)containing 29 balls (5 mm). The rotation speed of the planetary disk was set at 600 rpm and the reaction mixture ball-milled for the time specified. Rotation intervals (typically 5 min) were applied to ensure efficient mixing. At the conclusion of the reaction, the resulting solid was suspended in ethyl acetate and Na2SO4 was added. The mixture was filtered and the filtrate concentrated under reduced pressure to give a crude product that was purified by flash chromatography on silica gel eluting with the solvent(s) stated.
80%	With glacial acetic acid for 8h; Reflux;	1 Synthesis of intermediate M-1: in a 100ml there-necked flask, 0.01mol of phenylhydrazine hydrochloride was added to the acetic acid solution (30ml) containing 0.01mol of cyclohexanone in batches within 30 minutes, and then refluxed for 8 hours, The reaction is complete. The reaction solution was cooled to room temperature, then poured into ice water, filtered to obtain a crude product, and the solid was recrystallized from methanol to obtain a white solid M-1 (yield 80%).
70%	With glacial acetic acid for 2h; Reflux;
65%	In glacial acetic acid at 120℃; for 2h;
	With glacial acetic acid at 100℃;
	With 1,3,5-trichloro-2,4,6-triazine In ethanol at 80℃; for 2h;	General Experimental procedure General procedure: A mixture ofphenyl hydrazines.HCl (1 mmol), ketones (1 mmol) andTCT (0.1 mmol) in distilled ethanol was heated to 80 °C. After 2 h the startingmaterial was absent as monitored by TLC. The reaction mixture was cooled toambient temperature and diluted with water. The product was extracted intoethyl acetate (5x3 mL). The combined organiclayer was dried over anhydrous Na2SO4 and concentrated toresidue. Thus obtained residue was purified by column chromatography (gradientof 5-10 % EtOAc in Petroleum ether) to yield indole ortetrahydrocarbazole or tetrahydrocarboline derivatives (3a-3x).
	With glacial acetic acid at 100℃;
	With 1,3-bis(hydroxymethyl)urea at 80℃;
	With 4-(dimethylamino)-1-pentylpyridin-1-ium fluoride In ethanol at 78 - 80℃; Inert atmosphere;
	With sulfuric acid In lithium hydroxide monohydrate at 100℃; for 1.5h;
1.53 g	With glacial acetic acid for 2h; Reflux;
	With glacial acetic acid at 100℃; for 3h; Inert atmosphere;
	Stage #1: N-phenylhydrazine monohydrochloride With glacial acetic acid at 50℃; for 0.5h; Stage #2: cyclohexanone for 3h; Reflux;
	In tetrahydrofuran at 150℃; for 0.166667h; Microwave irradiation;

Yield	Reaction Conditions	Operation in experiment
96%	With hydrogen In methanol at 20℃; for 2h;
64%	With hydrogen In methanol at 22℃; for 18h;
60%	With hydrogen In methanol for 0.75h;

Yield	Reaction Conditions	Operation in experiment
92%	With [(IPr)Pd(acac)Cl]; potassium <i>tert</i>-butylate; magnesium sulfate In toluene at 100℃; for 12h; Inert atmosphere;
82%	With potassium phosphate; magnesium sulfate; acetic acid In N,N-dimethyl acetamide at 140℃; for 3h;
	Multi-step reaction with 2 steps 1: toluene / 16 h / Molecular sieve; Schlenk technique 2: (chloro)phenylallyl[1,3‐bis(2,6‐bis(diphenylmethyl)‐4‐methylphenyl)imidazo‐2‐ylidene]palladium(II); sodium t-butanolate / 1,4-dioxane / 24 h / 110 °C / Sealed tube; Inert atmosphere

Yield	Reaction Conditions	Operation in experiment
65%	Stage #1: 1,2,3,4-tetrahydrocarbazole With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 1,2-Epoxy-3-bromopropane In N,N-dimethyl-formamide at 20℃; for 6h;	9-Oxiranylmethyl-2,3,4,9-tetrahydro-1H-carbazole (6a), 6-methyl-9-oxiranylmethyl-2,3,4,9-tetrahydro-1H-carbazole (6b), 3,6-dimethyl-9-oxiranylmethyl-2,3,4,9-tetrahydro-1H-carbazole (6c), and 6-fluoro-9-oxiranylmethyl-2,3,4,9-tetrahydro-1H-carbazole (6d) (general procedure). General procedure: A solution of 1,2,3,4-tetrahydrocarbazole 8a-d (5.5 mmol) and KOH (5.5 mmol) in DMF (10 mL) was stirred for 1 h at 20 °C, compound 9 (10 mmol) was added, and the mixture was stirred for 6 h and poured into water (50 mL) to form an oily precipitate, which was extracted with dichloromethane. The solvent was evaporated and the residue was chromatographed on silica gel (60 mesh) using hexane-chloroform (4 : 1) as the eluent.
	With caesium carbonate In N,N-dimethyl-formamide at 60℃; for 15h;

Yield	Reaction Conditions	Operation in experiment
96%	With 1,1,1,3',3',3'-hexafluoro-propanol; RuBF₄((R,R)-N-Me-Tsdpen)(p-cymene); hydrogen at 30℃; for 31h; Autoclave; enantioselective reaction;
91%	With palladium(II) trifluoroacetate; 2,2,2-trifluoroethanol; (R)-10-camphorsulfonic acid; hydrogen; (R)-(+)-2,2'-bis(diphenylphosphanyl)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl In dichloromethane at 20℃; for 24h; Autoclave; optical yield given as %ee; enantioselective reaction;
91%	With (1S)-(+)-10-camphorsulfonic acid; C₄₆H₄₁F₃O₂P₂Pd; hydrogen In dichloromethane; 2,2,2-trifluoroethanol at 20℃; for 24h; Autoclave; Glovebox;

91%	With (RuOTf((R,R)-N-Me-Tsdpen)(p-cymene)); hydrogen at 25℃; for 24h; Inert atmosphere; Glovebox; Autoclave; enantioselective reaction;
	Multi-step reaction with 2 steps 1: tin; hydrogenchloride / ethanol; water / 4 h / 20 - 90 °C / Inert atmosphere 2: N-(1-phenyl-ethylidene)-(3,4,5-trimethoxy-phenyl)-amine; (R)-3,3'-bis(2,4,6-triisopropylphenyl)binol phosphoric acid / benzene / 20 h / 20 - 50 °C / Molecular sieve; Inert atmosphere

Yield	Reaction Conditions	Operation in experiment
97%	With hydrogenchloride; chloro(1,5-cyclooctadiene)rhodium(I) dimer; (S,R)-ZhaoPhos; hydrogen; acetic acid In dichloromethane at 25℃; for 48h; Autoclave; enantioselective reaction;
70%	With bis(1,5-cyclooctadiene)diiridium(I) dichloride; C₄₂H₃₄O₄P₂; camphor-10-sulfonic acid; hydrogen In 2-methyltetrahydrofuran at 20℃; for 20h; Autoclave; enantioselective reaction;
93 % ee	With palladium(II) trifluoroacetate; 5,5'-decamethylenedioxy-2,2'-bis(diphenylphosphino)biphenyl; (1S)-10-camphorsulfonic acid; hydrogen In dichloromethane at 35℃; for 24h; Autoclave; enantioselective reaction;	12 General procedure for Pd-catalyzed asymmetric hydrogenation General procedure: (S)-C10-BridgePHOS (2.0mg, 2.4mol%) and Pd(OCOCF3)2 (0.8mg, 2mol%) were placed into an oven dried flask under a nitrogen atmosphere, and degassed fresh dry acetone (2mL) was added. The mixture was stirred at room temperature for 1h. Then acetone was removed under vacuum and a solvent system of CH2Cl2/TFE (1/1, 1mL) was added to the mixture to afford the catalyst solution. The substrate 1 (0.15mmol) and additive (1equiv) were placed in a reaction tube under nitrogen and the above catalyst solution was added to the tube. The mixture was then degassed and transferred to a stainless steel autoclave in a glove box. After exchanging the gas three times, the hydrogenation was carried out at 35°C under 60bar H2. After several hours, the reaction mixture was concentrated under reduced pressure. After alkalization with saturated NaHCO3, the percentage conversion of product was determined by 1H NMR analysis of the crude product. The organic residue was purified by flash chromatography with ethyl acetate/petrol ether (1:50) to give pure product 2. Enantiomeric excess was determined using a Daicel Chiralcel column with hexane/i-propyl alcohol as the eluant.

Yield	Reaction Conditions	Operation in experiment
80%	With caesium carbonate In dimethyl sulfoxide at 70℃; for 15h; Inert atmosphere;
66%	With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 20℃; for 24h; Inert atmosphere;	2.2 Materials General procedure: 4, 4′-Difluorobenzophenone (99%), 2-phenylindole (95%), potassium tert-butoxide (99%), s 1, 2, 3, 4-tetrahydrocarbazole (99%), (all the materials sourced from Aldrich), were used as received. Thin layer chromatography was performed by using TLC plates covered with a silica gel matrix on aluminum backing (purchased from Aldrich). The general procedure was used for the synthesis of the following compounds. 4, 4′-Difluorobenzophenone (1.1mmol) and an N-heterocyclic compound (1, 2, 3, 4-tetrahydrocarbazole or 2-phenylindole) (2.2mmol) were dissolved in DMSO (8mL). Potassium tert-butoxide (11mmol) was added to the solution while vigorously stirring. The suspension mixture was stirred at room temperature for 24h under nitrogen atmosphere. The mixture was poured into ice-water (60mL) and filtered. The obtained crude product was purified by performing column chromatography on silica using ethylacetate:n-hexane mixture (1:3) as an eluent.Bis[4-(1,2,3,4-tetrahydrocarbazol-9-yl)phenyl]methanone (BTCM). The yield of yellowish crystals was 0.103 g (66%). MW = 520 g/mol. C37H32N2O. M.p. 168-169 °C. 1H NMR (400 MHz, CDCl3) δ 8.05 (s, 4H), 7.56 (s, 6H), 7.41 (s, 2H), 7.16 (s, 4H), 2.85 (s, 4H), 2.69 (s, 4H), 1.95 (s, 8H). 13C NMR (101 MHz, CDCl3) δ 194, 144, 136, 135, 132, 130, 128, 126, 121, 119, 117, 109, 31, 23, 21. ATR-IR (solid state on ATR, cm-1): 3048 (Ar. C-H), 2927 (Alk. C-H), 1569 (Ar. C=O) 1230 (Alk. C-N), 827 (Alk. C-H). MS: m/z 521 [(M+H)+].

Yield	Reaction Conditions	Operation in experiment
50%	With iron phtahlocyanine; oxygen In methanol at -40 - 20℃;
50%	With iron(II) phthalocyanine; oxygen In methanol at -40 - 20℃;	1 For the first embodiment, the product with the product number as indicated in the following table and having the general formula (V) was obtained by "direct coupling": In the first embodiment, compound (I) is usually reacted with compound (II) in the presence of a catalyst, for example iron phthalocyanine (FePc), and oxygen in a solvent such as methanol to yield product (IV), usually in a yield of more than 50%.

Yield	Reaction Conditions	Operation in experiment
94%	With zinc(II) chloride In 1,4-dioxane at 20 - 90℃; for 1h; Sealed tube; Inert atmosphere; regioselective reaction;
94%	With zinc(II) chloride In 1,4-dioxane at 90℃; for 4h;

Yield	Reaction Conditions	Operation in experiment
90%	With hydrogenchloride; titanium(III) chloride In water; acetonitrile at 20℃; for 8h; Inert atmosphere;
86%	With 1,2,2,3,4,4-hexamethylphosphetane 1-oxide; phenylsilane In acetic acid butyl ester at 120℃; for 8h; Schlenk technique; Inert atmosphere;
85%	With Triethoxysilane; C₂₅H₂₂FeNPS In 1,2-dimethoxyethane at 80℃; for 10h;

65%	With 3,4,7,8-Tetramethyl-o-phenanthrolin; palladium diacetate; molybdenum hexacarbonyl In N,N-dimethyl-formamide at 100℃; for 10h; Inert atmosphere; Sealed tube;
13%	With (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; triphenylphosphine In 1,4-dioxane at 55℃; for 96h; Inert atmosphere; Irradiation;	General procedure of the photochemical Cadogan cyclization General procedure: General Procedure A (GPA, Conditions A): A 20 mL reaction vessel was charged with 4CzIPN(3.2 mg, 0.004 mmol), nitro substrate (1a-1aw, 0.2 mmol), PPh3 (132 mg, 0.5 mmol) and1,4-dioxane (2.0 mL), The atmosphere was exchanged by applying vacuum and backfilling withAr (this process was conducted for three times). The resulting mixture was stirred for 2 d ~ 6 dunder irradiation with a 35 W blue LEDs at 55 C. The reaction was monitored by TLC. The crudereaction mixture was quenched with saturated sodium carbonate and extracted withdichloromethane (3×10 mL). The extracts were combined, dried over sodium sulfate, and filtered,and the volatiles were removed under reduced pressure. Column chromatography was performedusing silica gel (200-300 mesh) or thin layer chromatography was performed using silica gel(GF254) to give carbazole or indazole product.
46 mg	With triphenylphosphine In 1,4-dioxane at 160℃; for 24h; Inert atmosphere; Sealed tube;

Yield	Reaction Conditions	Operation in experiment
76%	With hydroquinone; cesium fluoride In N,N-dimethyl-formamide at 140℃; for 4h;	1-[3,7-Bis(dimethylamino)phenothiazin-10-yl]-3-(carbazol-9-yl)propane-1-one (5a). General procedure: A mixture of 1 mmol of carbazole 2a, 1 mmol of acrylate 1a, 0.1 g of CsF and 0.02 g of hydroquinone in 1.5 mL of DMF was stirred at 140°C for 12 h. The solvent was removed, and the residue was extracted with methylene chloride. Methylene chloride was evaporated, and the residue was purified by chromatography on silica gel (60 mesh, 1 : 5 methanol : chloroform mixture as eluent.
71%	With hydroquinone; cesium fluoride In N,N-dimethyl-formamide at 120 - 140℃; for 4h;	Synthesis of conjugates 14a,b, 15a-j, 16a,b and 17a,b (general procedure). General procedure: A stirred solution of acrylate 9 (1 mmol), cycloalkaneindole 10a,b, 11a-j, 12a,b, or 13a,b, (1 mmol), CsF (0.1 g), and hydroquinone (0.02 g) in DMF (1.5 mL) was heated at 120-140°C for 4 h. The solvent was removed in vacuo (3 Torr), the residue was extracted with dichloromethane, the solvent was removed in vacuo. Column chromatography of the residue (silica gel (60 mesh), elution with methanol-chloroform, 1 : 10) afforded target compounds. This procedure was applied for the synthesis of the following compounds: 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(2,3dihydro-1H-cyclopenta[b]indol-4-yl)propan-1-one hydrochloride (14a), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(7-methyl-2,3-dihydro-1H-cyclopenta[b]indol-4-yl)propan-1-one (14b), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15a), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(6-methyl-1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15b), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(6-fluoro-1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15c), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(6-methoxy-1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15d), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(6-trifluoromethoxy-1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15e), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(3-methyl-1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15f), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(3,6-dimethyl-1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15g), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(6-fluoro-3-methyl-1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15h), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(3-methyl-6-methoxy-1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15i), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(3methyl-6-trifluoromethoxy-1,2,3,4-tetrahydrocarbazol-9-yl)propan-1-one (15j), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(7,8,9,10-tetrahydro-6H-cyclohepta[b]indol-4-yl)propan-1-one (16a), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(2-methyl-7,8,9,10-tetrahydro-6H-cyclohepta[b]indol-4-yl)propan-1-one (16b), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(6,7,8,9,10,11-hexahydrocycloocta[b]indol-5-yl)propan-1-one (17a), 1-[3,7-bis(dimethylamino)phenothiazin-10-yl]-3-(2-methyl-6,7,8,9,10,11-hexahydrocycloocta[b]indol-5-yl)propan-1-one (17b).