81058-27-7

Basic information

• Product Name: 2,3,4,6-TETRA-O-PIVALOYL-ALPHA-D-GLUCOPYRANOSYL BROMIDE
• Synonyms: 2,3,4,6-TETRA-O-PIVALOYL-ALPHA-D-GLUCOPYRANOSYL BROMIDE;TETRAKIS(2,2-DIMETHYLPROPANOATE)-A-D-GLUCOPYRANOSYL BROMIDE;TETRA-O-PIVALOYL-ALPHA-D-GLUCOPYRANOSYL BROMIDE;2,3,4,6-Tetra-O-pivaloyl-a-D-glucopyranosylbromide;2,3,4,6-Tetra-O-pivaloyl-a-D-glucopyranosyl bromide (stabilised with CaCO3);[(2S,3S,4S,5R,6S)-6-broMo-3,4,5-tris(2,2-diMethylpropanoyloxy)tetrahydropyran-2-yl]Methyl2,2-diMethylpropanoate;4. 2,3,4,6-Tetra-O-pivaloyl-alpha-D-glucopyranosyl broMide;(2R,3R,4S,5R,6R)-2-BroMo-6-((pivaloyloxy)Methyl)tetrahydro-2H-pyran-3,4,5-triyl tris(2,2-diMethylpropanoate)
• CAS NO: 81058-27-7
• Molecular Formula: C₂₆H₄₃BrO₉
• Molecular Weight: 579.52
• EINECS: 686-241-8
• Product Categories: SGLT2;substrate;Canagliflozin intermediate
• Mol File: 81058-27-7.mol
• Article Data: 9

Chemical Properties

• Boiling Point: 530.5oC at 760 mmHg
• Flash Point: 274.6oC
• Appearance: /
• Density: 1.22g/cm3
• Vapor Pressure: 2.45E-11mmHg at 25°C
• Refractive Index: 1.494
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Sparingly)
• Stability: Light Sensitive, Moisture Sensitive
• CAS DataBase Reference: 2,3,4,6-TETRA-O-PIVALOYL-ALPHA-D-GLUCOPYRANOSYL BROMIDE(CAS DataBase Reference)
• NIST Chemistry Reference: 2,3,4,6-TETRA-O-PIVALOYL-ALPHA-D-GLUCOPYRANOSYL BROMIDE(81058-27-7)
• EPA Substance Registry System: 2,3,4,6-TETRA-O-PIVALOYL-ALPHA-D-GLUCOPYRANOSYL BROMIDE(81058-27-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• Hazardous Substances Data: 81058-27-7(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 81058-27-7 differently. You can refer to the following data:
1. 2,3,4,6-TETRA-O-PIVALOYL-ALPHA-D-GLUCOPYRANOSYL BROMIDE was used in the preparation of glucosylated monoterpenoids rhodiolosides A and D.
2. Tetra-O-pivaloyl-α-D-glucopyranosyl Bromide was used in the preparation of glucosylated monoterpenoids rhodiolosides A and D.
3. K?nigs-Knorr glycosyl donor with considerably lower tendency to form orthoester side products during glycosylation than the traditional acetobromoglucose

InChI:InChI=1/C26H43BrO9/c1-23(2,3)19(28)32-13-14-15(34-20(29)24(4,5)6)16(35-21(30)25(7,8)9)17(18(27)33-14)36-22(31)26(10,11)12/h14-18H,13H2,1-12H3/t14-,15-,16-,17+,18+/m0/s1

Synthetic route

1,2,3,4,6-penta-O-trimethylacetyl-β-D-glucopyranose (81058-26-6) → 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7)

Conditions	Yield
With bismuth(III) bromide; trimethylsilyl bromide In dichloromethane at 20℃; for 24h;	97%
With hydrogen bromide In dichloromethane; acetic acid for 12h;	64%
With hydrogen bromide; acetic acid In dichloromethane at 5℃; for 12h;	63%

1,2,3,4,6-penta-O-pivaloyl-D-glucopyranoside (1213234-53-7) → 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7)

Conditions	Yield
With trimethylsilyl bromide; zinc dibromide In dichloromethane at 10 - 25℃; Temperature; Inert atmosphere;	83%
Stage #1: 1,2,3,4,6-penta-O-pivaloyl-D-glucopyranoside With zinc dibromide In dichloromethane at 20℃; for 0.166667h; Inert atmosphere; Stage #2: With sodium hydrogencarbonate In dichloromethane; water
Stage #1: 1,2,3,4,6-penta-O-pivaloyl-D-glucopyranoside With trimethylsilyl bromide; zinc dibromide In dichloromethane at 20℃; for 24h; Inert atmosphere; Stage #2: With sodium hydrogencarbonate In dichloromethane; water at 0℃; pH=7 - 8;

1,2,3,4,6-penta-O-pivaloyl-D-glucopyranoside (114179-84-9) → 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7)

Conditions	Yield
With hydrogen bromide; acetic acid In dichloromethane at 0 - 20℃; for 3h;	70%
With hydrogen bromide; acetic acid In dichloromethane Molecular sieve;

pivaloyl chloride (3282-30-2) → 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 73 percent / Et3N; DMAP / CH2Cl2 / 24 h / 20 °C 2: 97 percent / BiBr3; Me3SiBr / CH2Cl2 / 24 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: 74 percent / pyridine / CHCl3 / 120 h / Ambient temperature 2: 64 percent / 40percent HBr / CH2Cl2; acetic acid / 12 h View Scheme
Multi-step reaction with 2 steps 1: triethylamine / dmap / dichloromethane / 0.75 h / 20 °C / Inert atmosphere 2: zinc dibromide / dichloromethane / 0.17 h / 20 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1.1: triethylamine / dmap / dichloromethane / 20.5 h / 0 - 20 °C / Inert atmosphere 2.1: trimethylsilyl bromide / zinc dibromide / dichloromethane / 24 h / 20 °C / Inert atmosphere 2.2: 0 °C / pH 7 - 8 View Scheme
Multi-step reaction with 2 steps 1: pyridine; dmap; thionyl chloride / dichloromethane / 2 h / 48 - 50 °C / Reflux; Large scale 2: zinc dibromide; trimethylsilyl bromide / dichloromethane / 10 - 25 °C / Inert atmosphere View Scheme

alpha-D-glucopyranose (492-62-6) → 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: triethylamine / dmap / dichloromethane / 20.5 h / 0 - 20 °C / Inert atmosphere 2.1: trimethylsilyl bromide / zinc dibromide / dichloromethane / 24 h / 20 °C / Inert atmosphere 2.2: 0 °C / pH 7 - 8 View Scheme
Multi-step reaction with 2 steps 1: pyridine; dmap; thionyl chloride / dichloromethane / 2 h / 48 - 50 °C / Reflux; Large scale 2: zinc dibromide; trimethylsilyl bromide / dichloromethane / 10 - 25 °C / Inert atmosphere View Scheme

pivaloyl chloride (3282-30-2) + ethyl α-D-glucopyranoside (3198-49-0, 15486-24-5, 18997-88-1, 19467-01-7, 34625-23-5, 59121-69-6, 118245-31-1, 118245-32-2, 142925-34-6) → 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7)

Conditions	Yield
In dichloromethane

D-glucose (50-99-7) + trimethylsilyl bromide (2857-97-8) → 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + pivaloyl chloride (3282-30-2)

Conditions	Yield
In dichloromethane
In dichloromethane
In dichloromethane

methyl-alpha-D-glucopyranoside (97-30-3) → 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + pivaloyl chloride (3282-30-2)

Conditions	Yield
With sodium bromide In dichloromethane

D-glucose (50-99-7) → 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + pivaloyl chloride (3282-30-2)

Conditions	Yield
With sodium bromide In dichloromethane

1-Tetradecanol (112-72-1) + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → tetradecyl 2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranoside (225641-98-5)

Conditions	Yield
With silver carbonate In diethyl ether	97%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → 3,4,6-tri-O-pivaloyl-D-glucal (149198-97-0, 104445-19-4)

Conditions	Yield
With acetic acid; zinc In tetrahydrofuran; water at 0 - 25℃; for 19.5h;	97%
With (2-) In water; N,N-dimethyl-formamide for 24h; pH 5.0;	90%

6-(2',4'-di(benzyloxy)phenyl)hexanol + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → 1-(2″,3″,4″,6″-tetra-O-pivaloyl-beta-D-glucopyranosyl)-4-(2,4-dibenzyloxyphenyl)hexane

Conditions	Yield
With silver carbonate In diethyl ether Koenigs-Knorr Glycosidation; Molecular sieve;	97%
With silver carbonate In diethyl ether Molecular sieve;	97%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + (1R)-4-[(3R)-3-(2,2-dimethyl-1-oxopropyloxy)]-3,5,5-trimethylcyclohex-3-enol (649723-26-2) → 2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-3,5-bis-(2,2-dimethyl-propionyloxy)-2-{(R)-4-[(R)-3-(2,2-dimethyl-propionyloxy)-butyl]-3,5,5-trimethyl-cyclohex-3-enyloxy}-6-(2,2-dimethyl-propionyloxymethyl)-tetrahydro-pyran-4-yl ester (649723-21-7)

Conditions	Yield
With 4 A molecular sieve; silver trifluoromethanesulfonate; tetramethylurea In dichloromethane at 0 - 20℃; for 2.5h;	96%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + Acetic acid (R)-4-((S)-3-hydroxy-but-1-ynyl)-3,5,5-trimethyl-cyclohex-3-enyl ester (322474-89-5) → 2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-2-[(S)-3-((R)-4-acetoxy-2,6,6-trimethyl-cyclohex-1-enyl)-1-methyl-prop-2-ynyloxy]-3,5-bis-(2,2-dimethyl-propionyloxy)-6-(2,2-dimethyl-propionyloxymethyl)-tetrahydro-pyran-4-yl ester (521291-38-3)

Conditions	Yield
With 4 A molecular sieve; silver trifluoromethanesulfonate; tetramethylurea In dichloromethane at 0 - 20℃; for 2.5h;	95%
With silver trifluoromethanesulfonate; tetramethylurea	72%

14-(2,4-di(benzyloxy)phenyl)tetradecanol + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → 1-(2″,3″,4″,6″-tetra-O-pivaloyl-beta-D-glucopyranosyl)-4-(2,4-dibenzyloxyphenyl)tetradecane

Conditions	Yield
With silver carbonate In diethyl ether Koenigs-Knorr Glycosidation; Molecular sieve;	95%
With silver carbonate In diethyl ether Molecular sieve;	95%

10-(2,4-di(benzyloxy)phenyl)decanol + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → C56H80O12

Conditions	Yield
With silver carbonate In diethyl ether Koenigs-Knorr Glycosidation;	94%
With silver carbonate In diethyl ether Molecular sieve;	94%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + phenol (108-95-2) → Phenyl-2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosid (100083-89-4)

Conditions	Yield
With silver(l) oxide In quinoline for 0.25h; Ambient temperature;	93%

C24H26O3 + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → C49H66O12

Conditions	Yield
With silver carbonate In diethyl ether at 20℃; Koenigs-Knorr Glycosidation;	93%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + 3-(2',4'-di(benzyloxy)phenyl)propanol (491610-75-4) → 1-(2″,3″,4″,6″-tetra-O-pivaloyl-beta-D-glucopyranosyl)-3-(2,4-dibenzyloxyphenyl)propane

Conditions	Yield
With silver carbonate In diethyl ether Koenigs-Knorr Glycosidation; Molecular sieve;	93%
With silver carbonate In diethyl ether for 4h; Molecular sieve;	93%

21-acetoxypregnenolone (566-78-9) + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → (21-Acetoxy-20-oxo-5-pregnen-3β-yl)-2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosid (100083-82-7)

Conditions	Yield
With molecular sieve; silver carbonate In diethyl ether for 20h; Ambient temperature;	92%

1-acetyl-1,2-dihydro-4-[(4-isopropoxyphenyl)methyl]-5-methyl-3H-pyrazol-3-one + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → 1-acetyl-4-[(4-isopropoxyphenyl)methyl]-5-methyl-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-1H-pyrazole

Conditions	Yield
With potassium carbonate In acetonitrile at 60℃; for 16h; Solvent; Reagent/catalyst;	92%

4-(2',4'-di(benzyloloxy)phenyl)butan-1-ol + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → 1-(2″,3″,4″,6″-tetra-O-pivaloyl-beta-D-glucopyranosyl)-4-(2,4-dibenzyloxyphenyl)butane

Conditions	Yield
With silver carbonate In diethyl ether Koenigs-Knorr Glycosidation; Molecular sieve;	92%
With silver carbonate In diethyl ether Molecular sieve;	92%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + C11H22F3NO3Si2 (101047-38-5, 107940-29-4) → 2,2-Dimethyl-propionic acid (2S,3S,4R,5R,6R)-4,5-bis-(2,2-dimethyl-propionyloxy)-6-(2,2-dimethyl-propionyloxymethyl)-2-[methoxycarbonyl-(2,2,2-trifluoro-acetylamino)-methyl]-tetrahydro-pyran-3-yl ester (129990-31-4, 129990-52-9)

Conditions	Yield
With zinc dibromide In 1,2-dichloro-ethane for 9h; Heating;	91%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + (-)-(8R/S,15R)-8-Benzyloxy-15-hydroxyhexadecansaeure-benzylester (133447-63-9, 133447-68-4) → (-)-(8R/S,15R)-8-Benzyloxy-15-<2,3,4,6-tetrakis-O-(2,2-dimethylpropanoyl)-β-D-glucopyranosyloxy>hexadecansaeure-benzylester (133470-51-6, 133574-67-1)

Conditions	Yield
With 3 A molecular sieve; silver carbonate In diethyl ether for 4h; Ambient temperature;	89%

1-Decanol (112-30-1) + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → decyl 2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranoside (225641-96-3)

Conditions	Yield
With silver carbonate In diethyl ether	89%

tigogenin (77-60-1) + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → <(25R)-5α-Spirostan-3β-yl>-2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosid (100102-42-9)

Conditions	Yield
With molecular sieve; silver carbonate In diethyl ether for 24h; Ambient temperature;	88%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + (R)-1-O-p-methoxybenzyloctadec-17-ene-1,3-diol (628316-30-3) → (3R)-1-O-(p-methoxybenzyl)-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyl)octadec-17-ene-1,3-diol (628316-31-4)

Conditions	Yield
With 2,6-di-tert-butyl-pyridine; silver trifluoromethanesulfonate In dichloromethane at -40 - -20℃; for 1.5h;	88%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + (+/-)-4-(4-benzyloxyphenyl)-2-butanol → C43H62O11

Conditions	Yield
With silver carbonate In diethyl ether at 20℃; Koenigs-Knorr Glycosidation;	88%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + (1R)-4-[(3R)-3-hydroxybutyl]-3,5,5-trimethylcyclohex-3-enyl (649723-25-1) → 2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-2-[(R)-3-((R)-4-acetoxy-2,6,6-trimethyl-cyclohex-1-enyl)-1-methyl-propoxy]-3,5-bis-(2,2-dimethyl-propionyloxy)-6-(2,2-dimethyl-propionyloxymethyl)-tetrahydro-pyran-4-yl ester (649723-23-9)

Conditions	Yield
With 4 A molecular sieve; silver trifluoromethanesulfonate; tetramethylurea In dichloromethane at 0 - 20℃; for 2.5h;	87%

(2-(4-fluorophenyl)-5-[(5-iodo-2-methylphenyl)methyl]thiophene) (898566-17-1) + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → (2S,3S,4R,5R,6R)-2-(3-((5-(4-fluorophenyl)thiophen-2-yl)methyl)-4-methylphenyl)-6-(pivaloyloxymethyl)tetrahydro-2H-pyran-3,4,5-thiyl tris(2,2-dimethylpropanoate) (1283129-18-9)

Conditions	Yield
Stage #1: (2-(4-fluorophenyl)-5-[(5-iodo-2-methylphenyl)methyl]thiophene) With n-butyllithium; zinc dibromide In n-heptane; dibutyl ether; toluene at -10 - 25℃; for 2.5h; Inert atmosphere; Stage #2: 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide In n-heptane; dibutyl ether; toluene at 95℃; for 6.5h; Product distribution / selectivity;	86.6%
Stage #1: (2-(4-fluorophenyl)-5-[(5-iodo-2-methylphenyl)methyl]thiophene) With TurboGrignard In tetrahydrofuran at 0 - 10℃; for 1h; Large scale; Stage #2: 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide In tetrahydrofuran at 0 - 10℃; for 3h; Large scale;	85%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + (8RS,15R)-8-acetoxy-1-benzyloxy-15-hexadecanol → (8RS,15R)-8-acetoxy-1-benzyloxy-15-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)hexadecane

Conditions	Yield
With 4 A molecular sieve; silver carbonate In diethyl ether for 24h; Ambient temperature;	86%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + benzyl alcohol (100-51-6) → benzyl 2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranoside (81058-28-8) + 1,2-O-(1-Benzyloxyneopentyliden)-3,4,6-tri-O-pivaloyl-α-D-glucopyranose (81058-29-9)

Conditions	Yield
With silver(II) oxide In diethyl ether for 5h; Ambient temperature;	A 86% B 1.3%

1-dodecyl alcohol (112-53-8) + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → dodecyl 2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranoside (225641-97-4)

Conditions	Yield
With silver carbonate In diethyl ether	85%

4,5-dihydroblumenol A (863032-33-1) + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → 2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-4,5-bis-(2,2-dimethyl-propionyloxy)-6-(2,2-dimethyl-propionyloxymethyl)-2-[(E)-(S)-3-((R)-1-hydroxy-2,6,6-trimethyl-4-oxo-cyclohex-2-enyl)-1-methyl-allyloxy]-tetrahydro-pyran-3-yl ester (863032-49-9)

Conditions	Yield
With silver trifluoromethanesulfonate; tetramethylurea In dichloromethane at 0 - 20℃; for 1.83333h;	85%

5-methyl-1-(propan-2-yl)-4-[4-(propan-2-yloxy)benzyl]-1,2-dihydro-3H-pyrazol-3-one (1028026-83-6) + 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → 4-[(4-isopropoxyphenyl)methyl]-1-isopropyl-5-methyl-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-1H-pyrazole

Conditions	Yield
With caesium carbonate In isopropyl alcohol; acetonitrile at 50℃; for 3h; Reagent/catalyst; Solvent;	85%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + di-4-methoxyphenylzinc (97302-05-1) → 2,3,4,6-tetra-O-pivaloyl 1-(2-anisyl)-1-deoxy-β-D-glucopyranose (1283129-20-3)

Conditions	Yield
In dibutyl ether; toluene at 90℃;	85%
With bis(pentafluorophenyl)zinc In (2)H8-toluene at 25℃; for 2h; Schlenk technique; Inert atmosphere; diastereoselective reaction;	99 %Spectr.

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) + methyl L-fucopyranoside (14687-15-1) → methyl 3-O-(2’,3’,4’,6’-tetra-O-pivaloyl-β-D-glucopyranosyl)-α-L-fucopyranoside (1330004-29-9)

Conditions	Yield
With [2-(1-methyl-1H-imidazol-2-yl)phenyl]boronic acid; silver(l) oxide In acetonitrile at 30℃; for 24h; Koenigs-Knorr Glycosidation; Inert atmosphere; regioselective reaction;	84%
With diphenylborate ethanolamine ester; silver(l) oxide In acetonitrile at 23℃; for 16h; Koenigs-Knorr synthesis; Inert atmosphere; regioselective reaction;	81%
Stage #1: methyl L-fucopyranoside With diphenyltin(IV) dichloride In acetonitrile at 20℃; for 0.166667h; Stage #2: 2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide With 5,5'-dimethyl-2,2'-bipyridine; silver(l) oxide In acetonitrile at 20 - 60℃; for 24h; Koenigs-Knorr Glycosidation; stereoselective reaction;	65%

2,3,4,6-tetra-O-pivaloyl-α-D-glucopyranosyl bromide (81058-27-7) → 2,3,4,6-tetra-O-pivaloyl-1,5-anhydro-D-arabino-hex-enitol (141514-11-6)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane for 4h; Ambient temperature;	83%

Upstream product

• 81058-26-6 1,2,3,4,6-penta-O-trimethylacetyl-β-D-glucopyranose 
• 3282-30-2 pivaloyl chloride 
• 114179-84-9 1,2,3,4,6-penta-O-pivaloyl-D-glucopyranoside 
• 1213234-53-7 1,2,3,4,6-penta-O-pivaloyl-D-glucopyranoside 
• 492-62-6 alpha-D-glucopyranose 
• 3198-49-0 ethyl α-D-glucopyranoside 
• 50-99-7 D-glucose 
• 2857-97-8 trimethylsilyl bromide 
• 97-30-3 methyl-alpha-D-glucopyranoside 

Downstream Products

• 184648-49-5 C₅₈H₈₈N₁₈O₂₁Si 
• 184648-43-9 (2R,3S,4S,5R,6R)-2-Hydroxymethyl-6-[(S)-3-(4-methoxy-benzyloxy)-1-methyl-propoxy]-tetrahydro-pyran-3,4,5-triol 
• 184648-44-0 (2R,3S,4S,5R,6R)-2-(tert-Butyl-dimethyl-silanyloxymethyl)-6-[(S)-3-(4-methoxy-benzyloxy)-1-methyl-propoxy]-tetrahydro-pyran-3,4,5-triol 
• 1053616-26-4 2,2-Dimethyl-propionic acid (2R,3R,4S,5R,6R)-4,5-bis-(2,2-dimethyl-propionyloxy)-6-(2,2-dimethyl-propionyloxymethyl)-2-[(S)-3-(4-methoxy-benzyloxy)-1-methyl-propoxy]-tetrahydro-pyran-3-yl ester 
• 184648-46-2 4-Azido-butyric acid (2R,3R,4S,5R,6R)-3,5-bis-(4-azido-butyryloxy)-2-hydroxymethyl-6-[(S)-3-(4-methoxy-benzyloxy)-1-methyl-propoxy]-tetrahydro-pyran-4-yl ester 
• 184648-45-1 4-Azido-butyric acid (2R,3R,4S,5R,6R)-3,5-bis-(4-azido-butyryloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-6-[(S)-3-(4-methoxy-benzyloxy)-1-methyl-propoxy]-tetrahydro-pyran-4-yl ester 
• 842133-18-0 canagliflozin 
• 1283129-18-9 (2S,3S,4R,5R,6R)-2-(3-((5-(4-fluorophenyl)thiophen-2-yl)methyl)-4-methylphenyl)-6-(pivaloyloxymethyl)tetrahydro-2H-pyran-3,4,5-triyl tris(2,2-dimethylpropanoate) 
• 329045-45-6 [14C]-Remogliflozin 
• 910054-55-6 4-[(4-isopropoxyphenyl)methyl]-5-methyl-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-1H-pyrazole 
• 1378263-86-5 C₃₉H₅₈N₂O₁₀ 
• 1064557-76-1 (4S)-2,6,6-trimethyl-4-O-(2',3',4',6'-tetrapivaloyl-β-D-glucopyranosyl)-cyclohex-2-en-1-one 

Relevant articles and documents

Excited-State Palladium-Catalyzed 1,2-Spin-Center Shift Enables Selective C-2 Reduction, Deuteration, and Iodination of Carbohydrates

Excited-state catalysis, a process that involves one or more excited catalytic species, has emerged as a powerful tool in organic synthesis because it allows access to the excited-state reaction landscape for the discovery of novel chemical reactivity. Herein, we report the first excited-state palladium-catalyzed 1,2-spin-center shift reaction that enables site-selective functionalization of carbohydrates. The strategy features mild reaction conditions with high levels of regio- and stereoselectivity that tolerate a wide range of functional groups and complex molecular architectures. Mechanistic studies suggest a radical mechanism involving the formation of hybrid palladium species that undergoes a 1,2-spin-center shift followed by the reduction, deuteration, and iodination to afford functionalized 2-deoxy sugars. The new reactivity will provide a general approach for the rapid generation of natural and unnatural carbohydrates.

Process for synthesizing card Geleg only (by machine translation)

The invention discloses a process for synthesizing card Geleg only, in order to 2?Methyl benzoic acid as starting material, use of improvised catalyst, reaction to produce the iodine iodate a in the middle, or in 2?Methyl benzoic acid as starting material, the metal reagent and under the action of catalyst, by adding liquid bromine, synthetic intermediates b; optionally intermediate one or intermediate two acylation reaction with thionyl chloride, to Friedel-crafts reaction produce intermediate three; in order to ALPHA?D?Glucose as raw material, with the reaction protection of all hydroxyl after pivalyl chloride, and then with zinc bromide, trimethyl silane reaction produce intermediate four; three intermediate the intermediate body, connecting delivery into intermediate five; finally under acidic conditions to remove the acyl special fifth heavenly stem, produce the target compound. card Geleg only of the present invention new process for the synthesis of high yield, mild condition, safety and reliability, is suitable for industrial production, raw material is cheap and easy to obtain, it is beneficial to control the production cost. (by machine translation)

PROCESS FOR THE PREPARATION OF COMPOUNDS USEFUL AS INHIBITORS OF SGLT2

The present invention is directed to a novel process for the preparation of compounds having inhibitory activity against sodium-dependent glucose transporter (SGLT) being present in the intestine or kidney.