196929-78-9

Basic information

• Product Name: (R)-(+)-2-Methyl-2-propanesulfinamide
• Synonyms: (R)-(+)-TERT-BUTANESULFINAMIDE;(R)-TERT-BUTANESULFINAMIDE;(R)-(+)-T-BUTANESULFINAMIDE;(R)-(+)-T-BUTYLMETHYLSULFINAMIDE;(R)-(+)-T-BUTYLSULFINAMIDE;(R)-(+)-TERT-BUTYLSULFINAMIDE;(R)-(+)-TERT-BUTYL SULPHINAMIDE;(R)-2-METHYLPROPANE-2-SULFINAMIDE
• CAS NO: 196929-78-9
• Molecular Formula: C₄H₁₁NOS
• Molecular Weight: 121.2
• EINECS: 1806241-263-5
• Product Categories: blocks;BuildingBlocks;Sulfonamides;chiral;Heterocyclic Compounds;CHIRAL COMPOUNDS;Asymmetric Synthesis;Sulfur Compounds (for Synthesis);Synthetic Organic Chemistry;CHIRAL CHEMICALS;Sulfur Compounds;Chiral Compound;Amines;Chiral Reagents;Intermediates;Sulfur & Selenium Compounds;Asymmetric Synthesis;Chiral Auxiliaries;Sulfur-Based;organosulfur compound
• Mol File: 196929-78-9.mol
• Article Data: 24

Chemical Properties

• Melting Point: 103-107 °C(lit.)
• Boiling Point: 219.957 °C at 760 mmHg
• Flash Point: -17℃
• Appearance: White, light pink, light yellow to brown/Powder
• Density: 0.903 g/mL at 25 °C
• Refractive Index: 4 ° (C=1, CHCl3)
• Storage Temp.: Keep Cold
• Solubility: Soluble in chloroform, methanol, tetrahydrofuran, dichloromethan
• PKA: 10.11±0.50(Predicted)
• Stability: store cold
• CAS DataBase Reference: (R)-(+)-2-Methyl-2-propanesulfinamide(CAS DataBase Reference)
• NIST Chemistry Reference: (R)-(+)-2-Methyl-2-propanesulfinamide(196929-78-9)
• EPA Substance Registry System: (R)-(+)-2-Methyl-2-propanesulfinamide(196929-78-9)

Safety Data

• Hazard Codes: Xi,Xn,F
• Statements: 11-19-36/37-40-36/37/38
• Safety Statements: 22-24/25-36/37-26-16-36/37/39
• RIDADR: UN 2056 3 / PGII
• WGK Germany: 3
• TSCA: No
• Hazardous Substances Data: 196929-78-9(Hazardous Substances Data)

Usage

Chemical Properties

(R)-(+)-2-Methyl-2-propanesulfinamide is white to light yellow crystal powde

Uses

Different sources of media describe the Uses of 196929-78-9 differently. You can refer to the following data:
1. suzuki reaction, useful reagent for synthesizing chiral amines.
2. (R)-(+)-2-Methyl-2-propanesulfinamide is a chiral ligand, which is used in pharmaceutical compositions. Further, it is used in the preparation of beta-chloro sulfinamides in the synthesis of chiral azridines. It is involved in the preparation of organocatalyst for enantioselective reduction of imines. It serves as a reagent for synthesizing chiral amines. In addition to this, it is converted into P,N-sulfinyl imine ligands through condensation with aldehydes and ketones which undergoes iridium-catalyzed asymmetric hydrogenation of olefins.
3. Chiral ligand used in pharmaceutical compositions

InChI:InChI=1/C6H17NS.H2O/c1-6(2,3)8(4,5)7;/h7H2,1-5H3;1H2

Synthetic route

(RS,S)-N-(3-hydroxy-1,3-diphenylpropylidene)-tert-butanesulfinamide (441788-45-0) → (S)-3-hydroxy-1,3-diphenyl-propan-1-one (42052-51-7, 69897-46-7, 72237-27-5, 93059-59-7) + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With acetic acid In methanol at 40℃; for 20h;	A 99% B n/a

(RS,S)-N-(3-hydroxy-4-methyl-1-phenylpentylidene)-tert-butanesulfinamide (441788-43-8) → (3S)-3-hydroxy-4-methyl-1-phenylpentan-4-one + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With acetic acid In methanol at 40℃; for 20h;	A 98% B n/a

(R)-4-chloro-2-((R)-1-(4-methylphenylsulfonamido)ethyl)phenyl 2-methylpropane-2-sulfinate → (R)-N-(1-(5-chloro-2-hydroxyphenyl)ethyl)-4-methylbenzenesulfonamide (1421840-44-9) + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran at -10℃; for 2.5h; Concentration; Temperature; Time; Inert atmosphere;	A 94% B 85%

(R)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-glucofuranos-3-yl tert-butanesulfinate (159263-57-7) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
Stage #1: (R)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-glucofuranos-3-yl tert-butanesulfinate With lithium hexamethyldisilazane In tetrahydrofuran at 0℃; for 48h; Inert atmosphere; Stage #2: With silica gel In tetrahydrofuran; methanol for 0.25h; Inert atmosphere;	92%
With aluminum oxide; potassium fluoride; lithium hexamethyldisilazane 1.) THF, from -78 deg C to RT, overnight, 2.) THF, 0 deg C, 1 h; Yield given. Multistep reaction;

2-Methyl-propane-2-sulfinic acid (1R,2S)-1-(2,4,6-trimethyl-benzenesulfonylamino)-indan-2-yl ester (861821-86-5) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With ammonia; lithium; ferric nitrate In tetrahydrofuran at -78℃; for 0.5h;	90%

2-Methyl-propane-2-sulfinic acid (1R,2S)-1-(2,4,6-trimethyl-benzenesulfonylamino)-indan-2-yl ester (446021-65-4) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With lithium amide; ammonia In tetrahydrofuran at -78℃;	90%

(4S,5R)-3-((S)-2-Methyl-propane-2-sulfinyl)-4,5-diphenyl-oxazolidin-2-one (813459-77-7) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With ammonia; lithium; ferric nitrate at -78℃; for 0.5h;	89%

(R)-tert-butylsulfinyl hydrazide → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With acetic acid; zinc In dichloromethane at 35 - 42℃; for 16h; Green chemistry;	83%
With acetic acid; zinc In dichloromethane at 35 - 42℃; for 16h;	83%
With acetic acid; zinc In dichloromethane at 35 - 42℃; for 16h;	83%

(RS)-N-benzyl-2-methylpropane-2-sulfinamide (212378-92-2) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With ammonia; lithium; ammonium chloride at -40℃; for 0.5h;	82%

(R)-DAG tert-butylsulfinate → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 48h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	80%

(R)-tert-butyl tert-butanethiosulfinate (67734-35-4) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With n-butyllithium; ammonia at -50 - 0℃; for 1h; Temperature; Concentration; Solvent;	79%
With lithium amide; ammonia at -78℃; for 0.25h;	77%
With Iron(III) nitrate nonahydrate; lithium amide; ammonia at -78℃;	48%
With lithium amide; ammonia In tetrahydrofuran at -78℃; Yield given;

(1S)-(6-methoxyquinolin-4-yl)(5-vinylquinuclidin-2-yl)methyl-(R)-2-tert-butylsulfinate → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With ammonia; lithium; ferric nitrate In tetrahydrofuran at -78℃; for 0.75h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	79%

quinine + tert-butylmagnesium chloride (677-22-5) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
Stage #1: quinine With thionyl chloride; triethylamine at -78 - -37℃; for 1h; Stage #2: tert-butylmagnesium chloride at -78 - 75℃; for 2h; Stage #3: With lithium hexamethyldisilazane	70%

2-fluoro-1-(2-fluorophenyl)ethan-1-one (1402412-84-3) → (R)-2-methyl-propane-2-sulfinic acid [2-fluoro-1-(2-fluoro-phenyl)-eth-(E)-ylidene]-amide (1415914-97-4) + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
	A 62% B n/a

di-tert-butyl disulfide (110-06-5) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
Stage #1: di-tert-butyl disulfide With bis(acetylacetonate)oxovanadium; (1S,2R)-1-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,3-dihydro-1H-inden-2-ol; dihydrogen peroxide In acetone at 0℃; Stage #2: With ammonia; lithium; ferric nitrate In tetrahydrofuran at -78℃;	60%

2-propyl tert-butanesulfinate (102101-45-1) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With Iron(III) nitrate nonahydrate; ammonia; lithium In 2-methyltetrahydrofuran at -65 - -50℃; Inert atmosphere;	60%

2-Methyl-propane-2-sulfinic acid ((R)-3-[1,3]dioxan-2-yl-1-phenyl-propyl)-amide (860640-13-7) → 2-phenyl-3,4-dihydro-2H-pyrrole + (R)-2-methylpropane-2-sulfinamide (196929-78-9) + trimethyleneglycol (504-63-2)

Conditions	Yield
With trifluoroacetic acid-d1 In water-d2 for 0.25h;

2-Methyl-propane-2-sulfinic acid (1R,2S)-1-(2,4,6-trimethyl-benzenesulfonylamino)-indan-2-yl ester (861821-86-5) → N-((1R,2S)-2-Hydroxy-indan-1-yl)-2,4,6-trimethyl-benzenesulfonamide (175848-32-5) + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With lithium amide; ammonia at -78℃;

ethyl tert-butanesulfinate (120424-96-6) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With ammonia; sodium; ferric nitrate In cyclopentyl methyl ether at -48 - 20℃; Inert atmosphere; optical yield given as %ee;	6.47 g

C21H29NO4S2 (1310105-98-6) → C17H21NO3S (620627-46-5) + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With lithium amide; ammonia at -60 - 20℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction;

phenyl 2-methylpropane-2-sulfinate → (R)-2-methylpropane-2-sulfinamide (196929-78-9) + phenol (108-95-2)

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 1.5h; Inert atmosphere;

phenyl 2-methylpropane-2-sulfinate → (R)-2-methylpropane-2-sulfinamide (196929-78-9) + (S)-2-methylpropane-2-sulfinamide (343338-28-3) + phenol (108-95-2)

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 1.5h; Inert atmosphere;	A n/a B n/a C n/a

4-chlorophenyl 2-methylpropane-2-sulfinate → 4-chloro-phenol (106-48-9) + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 1h; Inert atmosphere;

4-methoxyphenyl 2-methylpropane-2-sulfinate → 4-methoxy-phenol (150-76-5) + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; Inert atmosphere;

2,2,2-trifluoro-1-phenylethyl 2-methylpropane-2-sulfinate → 1-phenyl-2,2,2-trifluoromethylethanol (340-04-5, 340-05-6) + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 10h; Inert atmosphere;

1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-yl 2-methylpropane-2-sulfinate → 1,1,1,3,3,3-hexafluoro-2-(p-tolyl)propan-2-ol (2010-61-9) + (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 3h; Inert atmosphere;

tert-butyl tert-butanethiosulfinate (31562-40-0) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
Stage #1: tert-butyl tert-butanethiosulfinate With Iron(III) nitrate nonahydrate; ammonia; lithium In tetrahydrofuran at -78 - 20℃; for 16.75h; Inert atmosphere; Stage #2: With water; chloroacetic acid In tetrahydrofuran at 20℃; for 12.3333h; Inert atmosphere; Cooling with ice;

(+)-(S)-n-Propyl t-butylsulphinate (102101-42-8) → (R)-2-methylpropane-2-sulfinamide (196929-78-9)

Conditions	Yield
With Iron(III) nitrate nonahydrate; ammonia; sodium In tert-butyl methyl ether at -75 - -55℃; Inert atmosphere;	14.5 g

propionaldehyde (123-38-6) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-(-)-N-(propylidene)-2-methylpropane-2-sulfinamide (221375-47-9)

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 3h; Condensation;	100%
With magnesium sulfate In dichloromethane	96%
With copper(II) sulfate In dichloromethane for 20h; Inert atmosphere;	54%
With titanium(IV) isopropylate In tetrahydrofuran at 50℃;

3-methyl-butan-2-one (563-80-4) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-N-(3-methylbutan-2-ylidene)-2-methylpropane-2-sulfinamide (866993-51-3)

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 75℃;	100%
With titanium(IV) tetraethanolate In tetrahydrofuran Reflux;	75%
With titanium(IV) tetraethanolate In tetrahydrofuran at 60 - 75℃; Condensation;

3-phenyl-propionaldehyde (104-53-0) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (RS,E)-(-)-N-(3-phenylpropyl)idene-tert-butanesulfinamide (336105-29-4)

Conditions	Yield
With titanium(IV) tetraethanolate In dichloromethane at 20℃; for 1.5h;	100%
With titanium(IV) tetraethanolate In tetrahydrofuran; isopropyl alcohol for 5h;	91%
With pyridinium p-toluenesulfonate; magnesium sulfate In dichloromethane at 20℃; for 24h;	90%

butyraldehyde (123-72-8) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (RS,E)-N-butylidene-2-methylpropane-2-sulfinamide (479480-49-4)

Conditions	Yield
With molecular sieve; copper(II) sulfate In dichloromethane at 20℃;	100%
With pyridinium p-toluenesulfonate; magnesium sulfate In dichloromethane at 20℃; for 24h;	87%
With pyridinium p-toluenesulfonate; magnesium sulfate In dichloromethane at 20℃; for 20h;	85%

4-(4-fluoro-6-formyl-phenyl)-piperazine-1-carboxylic acid tert-butyl ester (697305-53-6) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → 4-{4-fluoro-2-[((RS)-2-methyl-propane-2-sulfinylimino)-methyl]-phenyl}-piperazine-1-carboxylic acid tert-butyl ester (869478-21-7)

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran; ethanol at 20℃; for 7h;	100%

4-(2-chloro-6-formyl-phenyl)-piperazine-1-carboxylic acid tert-butyl ester (869478-15-9) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → 4-{2-chloro-6-[((RS)-2-methyl-propane-2-sulfinylimino)-methyl]-phenyl}-piperazine-1-carboxylic acid tert-butyl ester

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran; ethanol at 20℃; for 24h;	100%

N-(4-acetyl-2,5-difluorophenyl)methanesulfonamide (910487-21-7) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → N-[4-((1R)-1-{[(R)-tert-butylsulfinyl]amino}ethyl)-2,5-difluorophenyl]methanesulfonamide (910487-22-8)

Conditions	Yield
Stage #1: N-(4-acetyl-2,5-difluorophenyl)methanesulfonamide; (R)-2-methylpropane-2-sulfinamide With titanium(IV) tetraethanolate In tetrahydrofuran at 70℃; for 30h; Stage #2: With sodium tetrahydroborate In tetrahydrofuran at 0 - 20℃; for 18h; Stage #3: With methanol; water In tetrahydrofuran	100%

N-(4-acetyl-2,6-difluorophenyl)methanesulfonamide (956901-21-6) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → N-[4-[(1R)-1-[[(R)-(1,1-dimethylethyl)sulfinyl]amino]ethyl]-2,6-difluorophenyl]methanesulfonamide (956901-22-7)

Conditions	Yield
Stage #1: N-(4-acetyl-2,6-difluorophenyl)methanesulfonamide; (R)-2-methylpropane-2-sulfinamide With titanium(IV) tetraethanolate In tetrahydrofuran at 70℃; for 18h; Stage #2: With sodium tetrahydroborate In tetrahydrofuran at -20 - 20℃; for 16h; Stage #3: With methanol; water In tetrahydrofuran	100%
Stage #1: N-(4-acetyl-2,6-difluorophenyl)methanesulfonamide; (R)-2-methylpropane-2-sulfinamide With titanium(IV) tetraethanolate In tetrahydrofuran at 70℃; for 18h; Stage #2: With sodium tetrahydroborate In tetrahydrofuran at -20 - 20℃; for 16h;	100%

ethyl 5-formyl-4-methyl-3-(pent-4-enyloxy)-1H-pyrrole-2-carboxylate (1020414-47-4) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-ethyl 4-methyl-5-[(2-methylpropan-2-ylsulfinyl)iminomethyl]-3-pent-4-enyloxy-1H-pyrrole-2-carboxylate (1020414-52-1)

Conditions	Yield
With titanium(IV) tetraethanolate In dichloromethane at 35℃; for 48h;	100%

(R)-2-methylpropane-2-sulfinamide (196929-78-9) + Cyclopropanecarboxaldehyde (1489-69-6) → [N(E),R(S)]-N-(cyclopropylmethylene)-2-methyl-2-propanesulfinamide (736947-01-6)

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 17h;	100%
With copper(II) sulfate In dichloromethane at 20℃; Inert atmosphere;	100%
With titanium(IV) tetraethanolate In tetrahydrofuran at 75℃; for 2h;	90%

isobutyraldehyde (78-84-2) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-N-(tert-butanesulfinyl)-N-(2-methylpropyliden)amine (196929-86-9)

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 24h; Inert atmosphere;	100%
With titanium(IV) tetraethanolate In tetrahydrofuran at 23℃; for 12h; Inert atmosphere;	82%
With titanium(IV) tetraethanolate at 70℃; for 0.166667h; Neat (no solvent); Microwave irradiation; Inert atmosphere;	53%

4-bromo-benzaldehyde (1122-91-4) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-N-(4-bromobenzylidene)-2-methylpropane-2-sulfinamide

Conditions	Yield
With titanium(IV) isopropylate In tetrahydrofuran at 20℃; for 16.0833h;	100%
With p-toluenesulfonic acid on sillica gel; water In neat (no solvent) for 0.5h; Sonication; Green chemistry;	95%
With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 16h; Inert atmosphere;

(3aS,6S,6aS)-2,2-dimethyl-6-vinyltetrahydrofuro[3,4-d][1,3]dioxol-4-ol + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-N-((3aS,4R,6S,6aS)-2,2-dimethyl-6-vinyl-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl)-2-methylpropane-2-sulfinamide (1359756-29-8)

Conditions	Yield
With caesium carbonate In dichloromethane for 3h; Reflux; Inert atmosphere; stereospecific reaction;	100%

4-chloro-3-fluoro-2-formylpyridine (1260878-78-1) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (S,E)-N-((4-chloro-3-fluoropyridin-2-yl)methylene)-2-methylpropane-2-sulfinamide (1422510-26-6)

Conditions	Yield
With caesium carbonate In dichloromethane at 20℃; for 1h;	100%

4-cyanobenzaldehyde (105-07-7) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-(-)-N-(4-cyanobenzylidene)-2-methylpropane-2-sulfinamide (935263-24-4)

Conditions	Yield
With caesium carbonate In dichloromethane for 1h; Reflux;	100%
With p-toluenesulfonic acid on sillica gel In neat (no solvent) for 0.5h; Sonication; Green chemistry;	95%
With tetrafluoroboric acid diethyl ether; magnesium sulfate In dichloromethane at 20℃; for 2h;	91%

5-bromopyridine-3-carbaldehyde (113118-81-3) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-N-[(1E)-(5-chloropyridin-3-yl)methylidene]-2-methylpropane-2-sulfinamide

Conditions	Yield
With caesium carbonate In dichloromethane at 20℃;	100%

1-(benzo[d][1,3]dioxol-6-yl)ethanone (3162-29-6) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-N-(1-(benzo[d][1,3]dioxol-5-yl)ethylidene)-2-methylpropane-2-sulfinamide

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 30h; Time; Reflux;	100%
With titanium(IV) tetraethanolate In tetrahydrofuran for 35.5h; Reflux;
With titanium (IV) ethoxide In tetrahydrofuran at 20℃; for 35.5h; Reflux;
With titanium(IV) tetraethanolate In tetrahydrofuran at 65℃; for 6h; Inert atmosphere;

6-chloro-7-fluoro-2-oxo-1,2-dihydroquinoline-3-carbaldehyde + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R,E)-N-((6-chloro-7-fluoro-2-oxo-1,2-dihydroquinolin-3-yl)methylene)-2-methylpropane-2-sulfinamide

Conditions	Yield
With titanium(IV) isopropylate In tetrahydrofuran at 20℃; for 24h; Inert atmosphere;	100%

1-tert-butoxycarbonyl-3-formylindole (57476-50-3) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R,E)-tert-butyl 3-(((tert-butylsulfinyl)imino)methyl)-1H-indole-1-carboxylate

Conditions	Yield
With titanium(IV) tetraethanolate at 20℃; for 12h; Inert atmosphere;	100%
With titanium (IV) ethoxide In tetrahydrofuran at 20℃; for 12h;	89%

allyl-N-methyl-N-(3-oxopropyl)carbamate + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (E)-allyl (3-((tert-butylsulfinyl)imino)propyl)(methyl)carbamate

Conditions	Yield
With pyridinium p-toluenesulfonate; magnesium sulfate In dichloromethane at 20℃;	100%

3-phenyl-propenal (104-55-2) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (RS,E,E)-(-)-N-(3-phenylpropenyl)idene-tert-butanesulfinamide (364364-07-8)

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; Inert atmosphere;	100%

isoquinoline-8-carboxaldehyde (787615-01-4) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-N-(isoquinolin-8-ylmethylene)-2-methylpropane-2-sulfinamide

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 4h;	100%

2-chloro-6-fluorobenzaldehyde (387-45-1) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R,E)-N-(2-chloro-6-fluorobenzylidene)-2-methylpropane-2-sulfinamide

Conditions	Yield
With caesium carbonate In dichloromethane at 20℃; for 17h;	100%

(S)-3-phenylcyclopentanone (64145-51-3, 86505-44-4, 141662-68-2, 86505-50-2) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → C15H21NOS

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 75℃;	100%

4-chloro-3-fluoro-2-formylpyridine (1260878-78-1) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (±)-(E)-N-((4-chloro-3-fluoropyridin-2-yl)methylene)-2-methylpropane-2-sulfinamide

Conditions	Yield
With caesium carbonate In dichloromethane at 20℃; for 1h;	100%

(R)-2-methylpropane-2-sulfinamide (196929-78-9) + 3-(cyclopropylmethoxy)-4-(difluoromethoxy)-benzaldehyde (151103-09-2) → (R)-2-methyl-2-propanesulfinic acid 3-cyclopropylmethoxy-4-(difluoromethoxy)benzylideneamide (1367625-78-2)

Conditions	Yield
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 12h;	99.8%

4-chlorobenzaldehyde (104-88-1) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-(-)-N-[(1E)-(4-chlorophenyl)methylene]-2-methyl-2-propanesulfinamide (336105-23-8)

Conditions	Yield
With pyridinium p-toluenesulfonate; magnesium sulfate In dichloromethane at 20℃;	99%
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; Ellmann's method;	95%
With titanium(IV) tetraethanolate In tetrahydrofuran at 22℃;	90%
With titanium(IV) tetraethanolate In dichloromethane at 20℃;
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃;

1-naphthaldehyde (66-77-3) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-(-)-2-methyl-N-[(1E)-1-naphthalenylmethylene]-2-propanesulfinamide (451503-13-2)

Conditions	Yield
With pyridinium p-toluenesulfonate; magnesium sulfate In dichloromethane at 20℃;	99%

benzaldehyde (100-52-7) + (R)-2-methylpropane-2-sulfinamide (196929-78-9) → (R)-N-benzylidene-2-methylpropane-2-sulfinamide (196929-85-8)

Conditions	Yield
With titanium(IV) tetraethanolate at 70℃; for 0.166667h; Neat (no solvent); Microwave irradiation; Inert atmosphere;	99%
With copper(II) sulfate In dichloromethane at 20℃;	99%
With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 24h; Inert atmosphere;	99%

Upstream product

• 120424-96-6 ethyl tert-butanesulfinate 
• 1310105-98-6 C₂₁H₂₉NO₄S₂ 
• 102101-45-1 2-propyl tert-butanesulfinate 
• 102101-42-8 (-)-(S)-n-propyl t-butylsulphinate 
• 31562-40-0 tert-butyl tert-butanethiosulfinate 
• 677-22-5 tert-butylmagnesium chloride 
• 861821-86-5 2-Methyl-propane-2-sulfinic acid (1R,2S)-1-(2,4,6-trimethyl-benzenesulfonylamino)-indan-2-yl ester 
• 860640-13-7 2-Methyl-propane-2-sulfinic acid ((R)-3-[1,3]dioxan-2-yl-1-phenyl-propyl)-amide 
• 813459-77-7 (4S,5R)-3-((S)-2-Methyl-propane-2-sulfinyl)-4,5-diphenyl-oxazolidin-2-one 
• 446021-65-4 2-Methyl-propane-2-sulfinic acid (1R,2S)-1-(2,4,6-trimethyl-benzenesulfonylamino)-indan-2-yl ester 
• 441788-45-0 (R_S,S)-N-(3-hydroxy-1,3-diphenylpropylidene)-tert-butanesulfinamide 
• 441788-43-8 (R_S,S)-N-(3-hydroxy-4-methyl-1-phenylpentylidene)-tert-butanesulfinamide 
• 110-06-5 di-tert-butyl disulfide 
• 159263-57-7 (R)-3-deoxy-1,2:5,6-di-O-isopropylidene-α-D-glucofuranos-3-yl tert-butanesulfinate 

Downstream Products

• 336105-24-9 (R)-(-)-N-[(1E)-(4-bromophenyl)methylene]-2-methyl-2-propanesulfinamide 
• 700828-08-6 2-methyl-propane-2-sulfinic acid (4-methyl-cyclohexylidene)-amide 
• 700828-06-4 2-methyl-propane-2-sulfinic acid (4-tert-butyl-cyclohexylidene)-amide 
• 927386-24-1 (R_S)-(-)-N-[1-(1-chlorocyclohexyl)ethylidene]-tert-butanesulfinamide 
• 909711-12-2 ethyl 5-((1R)-1-{[(R)-tert-butylsulfinyl]amino}ethyl)-2-[(methyl-sulfonyl)amino]benzoate 
• 910487-22-8 N-[4-((1R)-1-{[(R)-tert-butylsulfinyl]amino}ethyl)-2,5-difluorophenyl]methanesulfonamide 
• 956901-22-7 N-[4-[(1R)-1-[[(R)-(1,1-dimethylethyl)sulfinyl]amino]ethyl]-2,6-difluorophenyl]methanesulfonamide 
• 910487-81-9 N-[2-(2-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}ethyl)-4-((1R)-1-{[(R)-(1,1-dimethylethyl)sulfinyl]amino}ethyl)phenyl]methanesulfonamide 
• 910487-87-5 N-{4-[(1R)-1-aminopropyl]-2-ethylphenyl}methanesulfonamide 
• 910487-96-6 N-[4-(1-{[(R)-tert-butylsulfinyl]imino}ethyl)-5-fluoro-2-methyl-phenyl]methanesulfonamide 
• 1001022-85-0 (R)-N-((1R,2R)-2-(dimethylamino)cyclohexylcarbamoyl)-tert-butanesulfinamide 
• 1001022-80-5 (R)-N-(phenylcarbamoyl)-tert-butanesulfinamide 

Relevant articles and documents

Improved synthesis of tert-butanesulfinamide suitable for large-scale production

(Matrix presented) An improved synthesis of tert-butanesulfinamide that overcomes the scalability problems of the previous syntheses is described. The key step is the catalytic asymmetric oxidation of the inexpensive di-tert-butyl disulfide starting material. The new homogeneous reaction conditions utilize an inexpensive chiral ligand prepared in a single step from commercially available cis-1-amino-indan-2-ol. The reaction is performed at a 2.3 M concentration in the practical solvent acetone and can readily be run on a kilogram scale.

Method for preparing chiral tert-butyl sulfinamide

The invention belongs to the technical field of chemical synthesis, and provides a method for preparing (R)-tert-butyl sulfinamide. The method comprises the following steps: (1) preparing a Grignard compound by using halogenated tert-butane as an initial raw material through a Grignard reaction, introducing sulfur dioxide gas into the Grignard reaction solution, and reacting to obtain tert-butyl sulfinic acid; (2) converting tert-butyl sulfinic acid into tert-butyl sulfinyl chloride by adopting thionyl chloride; (3) converting tert-butyl sulfinyl chloride into tert-butyl sulfinate through an alcohol reagent and an alkaloid compound; and (4) converting tert-butyl sulfinate into chiral (R)-tert-butyl sulfinate amine in the presence of ferric nitrate, lithium metal or sodium metal. Accordingto the method, the defects of an existing process are overcome, foul tert-butyl mercaptan is not used, used halogenated tert-butane and the like are common and cheap materials, alkaloid compounds canbe recycled, and the method is more suitable for industrial production.

Method for preparing enantiomer pure methylpropane-2-sulfinamide

The invention discloses a method for preparing enantiomer pure methylpropane-2-sulfinamide. The method comprises the following steps: performing selective oxidation on tertiary butyl dithioether and hydrogen peroxide; adding an acylation reagent so as to obtain tertiary butyl sulfonyl chloride or tertiary butyl thionyl bromide; adding hydrazine hydrate so as to obtain tertiary butyl thionyl hydrazine; further performing resolving dissociation with a tartaric acid resolving agent; performing cracking with zinc acetate, thereby obtaining the enantiomer pure methylpropane-2-sulfinamide. The method is simple and stable in process operation, high in yield and good in environment protection, and compared with a conventional process, the method is low in raw material price, easy in raw material obtaining, capable of reducing the production cost of conventional enantiomer pure methylpropane-2-sulfinamide, and beneficial to industrial on-scale production.

Process for synthesizing chiral tert-butanesulfinyl amide

The invention discloses a process for synthesizing chiral tert-butanesulfinyl amide. The process includes carrying out reaction on tert-butyl mercaptan and iodine/hydrogen peroxide acetone to generate di-tert-butyl disulfide; oxidizing hydrogen peroxide under the catalytic effect of vanadium to generate chiral tert-butyl sulfenyl tert-butyl mercaptide; carrying out one-pot reaction on the chiral tert-butyl sulfenyl tert-butyl mercaptide and lithium reagents/liquid ammonia in the presence of alkyl chloride to obtain the tert-butanesulfinyl amide. Compared with existing processes, the process has the advantages that the smoothness of the process can be enhanced, the usage of the liquid ammonia can be reduced to a great extent, and the operational efficiency can be improved.