1139-30-6

Basic information

• Product Name: CARYOPHYLLENE OXIDE
• Synonyms: (-)-5-Oxatricyclo[8.2.0.0(4,6)]dodecane,4,12,12-trimethyl-9-methylene-, [1R-(1R*,4R*,6R*,10S*)]-;(-)-beta-Caryophyllene epoxide;(-)-beta-caryophylleneepoxid;(-)-beta-caryophylleneepoxide;(-)-Epoxydihydrocaryophyllene;(1r-(1r*,4r*,6r*,10s*))-4,12,12-trimethyl-9-methylene-5-oxatricyclo(8.2.0.04,6)dodecane;(1r-(1r,4r,6r,10s))-4,12,12-trimethyl;(1r-(1r,4r,6r,10s))-4,12,12-trimethyl-9-methylene-5-oxatricyclo(8.2.0.04,6)dodecane
• CAS NO: 1139-30-6
• Molecular Formula: C₁₅H₂₄O
• Molecular Weight: 220.35
• EINECS: 214-519-7
• Product Categories: Alphabetical Listings;C-D;Flavors and Fragrances;Inhibitors;Sesquiterpenoids
• Mol File: 1139-30-6.mol
• Article Data: 23

Chemical Properties

• Melting Point: 62-63 °C(lit.)
• Boiling Point: 301.3°C (rough estimate)
• Flash Point: >230 °F
• Appearance: White/Crystalline Powder
• Density: 0.96
• Vapor Pressure: 0.00672mmHg at 25°C
• Refractive Index: 1.4956
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• BRN: 148213
• CAS DataBase Reference: CARYOPHYLLENE OXIDE(CAS DataBase Reference)
• NIST Chemistry Reference: CARYOPHYLLENE OXIDE(1139-30-6)
• EPA Substance Registry System: CARYOPHYLLENE OXIDE(1139-30-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/38
• Safety Statements: 26
• WGK Germany: 2
• RTECS: RP5530000
• F: 1-10
• Hazardous Substances Data: 1139-30-6(Hazardous Substances Data)

Usage

Chemical Properties

Different sources of media describe the Chemical Properties of 1139-30-6 differently. You can refer to the following data:
1. white crystalline powder
2. Caryophyllene oxide which has a woody, slightly ambergris-like odor, can be prepared by treatment of ??-caryophyllene with organic peracids.
3. Colorless solid; sweet fruity aroma.

Occurrence

Reported found in Nepeta betonicifolia C.A. Meyer oil Turkey (39.20%), geranium rose-scented oil (Pelargonium spp.) Cuba (14.70%), melissa oil (9.99%), guava leaf oil Cuba (8.20%), etc.

Uses

β-Caryophyllene Epoxide, and its derivatives has shown to have microbial transformation and butyrylcholinesterase inhibitory activity. It is also the main active constituent of essential oils obtained from various plants, used for flavoring and fragrances.

Definition

ChEBI: A natural product found in Cupania cinerea.

Aroma threshold values

Medium strength odor, woody type.

Safety Profile

Low toxicity by ingestion and skin contact. A skin irritant. When heated to decomposition it emits acrid smoke and irritating fumes.

Purification Methods

Purify the oxide by TLC on silica gel with EtOAc/pet ether (b 60-80o) (15:85), and recrystallise it from MeOH or *C6H6. [NMR: Warnhoff Can J Chem 42 1664 1964, Ramage & Whitehead J Chem Soc 4336 1954, Beilstein 17 IV 392.]

InChI:InChI=1/C15H24O/c1-10-5-6-13-15(4,16-13)8-7-12-11(10)9-14(12,2)3/h11-13H,1,5-9H2,2-4H3/t11-,12-,13-,15+/m0/s1

Synthetic route

Methyltriphenylphosphonium bromide (1779-49-3) + (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodcan-9-one (10306-22-6, 10306-31-7, 24173-71-5, 34175-71-8) → caryophyllene oxide (1139-30-6)

Conditions	Yield
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 0.166667h; Stage #2: (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodcan-9-one In tetrahydrofuran at -78 - 20℃; for 24h;	74%

β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6)

Conditions	Yield
With 4-methyloxetan-2-one; CpLIP2 Y179F (ipase/acyltransferase) from Candida parapsilosis; dihydrogen peroxide In aq. phosphate buffer; water at 20℃; for 24h; pH=6.5; Reagent/catalyst; Enzymatic reaction;	67%
With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 2h;	66%
With peracetic acid; sodium acetate In dichloromethane
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 0.5h;	75 % Chromat.

Perbenzoic acid (93-59-4) + β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6)

Conditions	Yield
With chloroform

monoperoxyphthalic acid (2311-91-3) + β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6)

Conditions	Yield
With diethyl ether

β-caryophyllene (87-44-5) → (1R,4R,5R,9S,11R)-4,5-epoxy-12-nor-8(14)-caryophyllene-11-ol (118122-82-0) + (1R,4R,5R,9S,11R)-4,5-epoxy-caryophyll-8(14)-en-12-oic acid (108525-13-9) + 15-hydroxycaryophyllene oxide (73510-14-2) + caryophyllene oxide (1139-30-6)

Conditions	Yield
for 72h; Diplodia gossypina ATCC 10936; Further byproducts given;	A 220 mg B 900 mg C 300 mg D 65 mg

β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6) + (5S,6S)-5,6-epoxy-5,6-dihydrocaryophyllene (103475-43-0)

Conditions	Yield
With peracetic acid; sodium acetate In dichloromethane at 0℃; Yield given. Yields of byproduct given;
With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 2h; Title compound not separated from byproducts;	A 81 % Spectr. B 19 % Spectr.
With peracetic acid; sodium acetate In dichloromethane at 0℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

β-caryophyllene (87-44-5) → caryophyllene oxide (1139-30-6) + (2R,5R,6R)-2,12:5,6-diepoxycaryophyllane (60444-80-6) + (1R,4R,6R,9S,10S)-4,12,12-trimethylspiro(5-oxatricyclo[8.2.0.04,6]dodecane-9,2'-oxirane) (60479-10-9)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 0.5h; Product distribution; effect of stoichiometry, temperature, reaction time;	A 52 % Chromat. B 21 % Chromat. C 21 % Chromat.

5,6-epoxy-2-hydroxymethyl-6,10,10-trimethyl-bicyclo[7.2.0]undecan-2-ol (10577-25-0, 60479-11-0, 60479-16-5, 60479-18-7, 123808-25-3) → caryophyllene oxide (1139-30-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sodium periodate / water; methanol / 4.33 h / 20 °C / Inert atmosphere 2.1: n-butyllithium / tetrahydrofuran / 0.17 h / -78 - 0 °C 2.2: 24 h / -78 - 20 °C View Scheme

caryophyllene oxide (1139-30-6) → 1,5,5,8-tetramethyl-[1R-(1R*,3E,7E,11R*)]-12-oxabicyclo[9.1.0]dodeca-3,7-diene (19888-34-7, 67737-67-1, 90820-79-4, 108101-44-6)

Conditions	Yield
With phenylsilane In benzene for 2h;	100%
With (+/-)-trans-Co(III)-salen-Cl; phenylsilane In benzene for 2h;	100%
With C32H46ClCoN2O2; phenylsilane In benzene at 22℃; for 5h; Inert atmosphere;	95%

caryophyllene oxide (1139-30-6) → (-)-humulene epoxide II

Conditions	Yield
With (+/-)-trans-Co(III)-salen-Cl; phenylsilane In benzene for 2h;	100%

caryophyllene oxide (1139-30-6) → (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodcan-9-one (10306-22-6, 10306-31-7, 24173-71-5, 34175-71-8)

Conditions	Yield
Stage #1: caryophyllene oxide With ozone In dichloromethane at -78℃; Stage #2: With acetic acid; zinc In dichloromethane; water at 20℃; for 18h; Inert atmosphere;	98%
With ruthenium trichloride; sodium periodate In water; ethyl acetate; acetonitrile for 6h;	61%
With ruthenium trichloride; sodium periodate; water In ethyl acetate; acetonitrile for 6h;	61%

6-(trimethylsilyl)hex-5-yn-1-yl 2-cyano-2-diazoacetate (1361382-43-5) + caryophyllene oxide (1139-30-6) → C27H41NO3Si

Conditions	Yield
With Rh2(esp)2 In dichloromethane at 22℃; for 4h; Inert atmosphere; diastereoselective reaction;	94%

caryophyllene oxide (1139-30-6) → 1R,5S,9S-11,11-dimethyl-4,8-bismethylenebicyclo<7.2.0>undecan-5-ol (19431-79-9)

Conditions	Yield
With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane Heating;	90%
With n-butyllithium In diethyl ether
With ethenetetracarbonitrile; lithium bromide In acetone
With ethenetetracarbonitrile; lithium bromide In acetone

caryophyllene oxide (1139-30-6) → ((1R,4R,6R,9S,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodecan-9-yl)methanol

Conditions	Yield
Stage #1: caryophyllene oxide With 9-bora-bicyclo[3.3.1]nonane In tetrahydrofuran for 8h; Inert atmosphere; Cooling with ice; Stage #2: With dihydrogen peroxide; sodium hydroxide In tetrahydrofuran at 20℃; for 2h;	90%

caryophyllene oxide (1139-30-6) + thioacetic acid (507-09-5) → ({(1R,4R,6R,9R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.04,6]dodec-9-yl}methyl)ethanethioate

Conditions	Yield
With silica gel regioselective reaction;	89%

caryophyllene oxide (1139-30-6) → 5,6-epoxy-2-hydroxymethyl-6,10,10-trimethyl-bicyclo[7.2.0]undecan-2-ol (10577-25-0, 60479-11-0, 60479-16-5, 60479-18-7, 123808-25-3)

Conditions	Yield
With osmium(VIII) oxide; 4-methylmorpholine N-oxide In water; tert-butyl alcohol at 20℃; for 70h;	82%

2-bromo-1,3-thiazole (3034-53-5) + caryophyllene oxide (1139-30-6) → 2-(((1S,11S,Z)-7,7,11-trimethyl-12-oxabicyclo[9.1.0]dodec-4-en-4-yl)methyl)thiazole

Conditions	Yield
With formic acid; tributyl-amine; tris[2-phenylpyridinato-C2,N]iridium(III) In acetonitrile at 45℃; for 19h; Inert atmosphere; Irradiation; Sealed tube; diastereoselective reaction;	71%

caryophyllene oxide (1139-30-6) → (1R,2S,5R,8S,9R)-1,4,4,8-tetramethyltricyclo[6.3.0.02,5]undecan-9-ol (122621-21-0) + (1S,2S,5R,8R,9R)-1,4,4,8-tetramethyltricyclo[6.3.0.02,5]undecan-9-ol (122571-86-2)

Conditions	Yield
With 2,4,6-trimethyl-pyridine; manganese; chloro-trimethyl-silane; bis(cyclopentadienyl)titanium dichloride In tetrahydrofuran at 20℃; for 0.666667h;	A 65% B 30%

caryophyllene oxide (1139-30-6) + 2-methylpropan-2-thiol (75-66-1) → clovanediol (2649-64-1) + (1S,2S,5S,8R,9R)-2-tert-butylsulfanyl-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecan-9-ol + 4,10,10-trimethyl-7-methylene-1β,8α-bicyclo[6.2.0]decene-4-carboxaldehyde (475285-25-7)

Conditions	Yield
With zinc(II) chloride In dichloromethane Reflux;	A 6% B 63% C 7%

Iodoethanol (624-76-0) + caryophyllene oxide (1139-30-6) → 2β-(2-iodoethoxy)clovan-9α-ol (1112901-60-6)

Conditions	Yield
With ethenetetracarbonitrile at 25℃;	62%

caryophyllene oxide (1139-30-6) → 4,9,12,12-tetramethyl-5-oxatricyclo[8.2.0.04,6]dodecan-9-ol (103189-78-2)

Conditions	Yield
With iron(III)-acetylacetonate; methyl 4-nitrobenzenesulfonate; phenylsilane; sodium hydrogencarbonate In methanol at 0 - 20℃; for 12h; Schlenk technique; Inert atmosphere; diastereoselective reaction;	62%

caryophyllene oxide (1139-30-6) → (1R,5S,8R,9R)-4,4,8-trimethylbicyclo<6.3.1.01,5>dodeca-2-en-9-ol (92760-17-3)

Conditions	Yield
With bithmuth(III) triflate hydrate In dichloromethane for 0.166667h; Wagner-Meerwein rearrangement; Reflux;	60%
With methanol; fluorosulfonylchloride; fluorosulphonic acid 1.) -100 deg C, 2.) diethyl ether; Yield given. Multistep reaction;

caryophyllene oxide (1139-30-6) + phenylmethanethiol (100-53-8) → (1S,2S,6S,9R)-2-(benzylsulfanyl)-6,2,10,10-tetramethylbicyclo[7.2.0]undecan-5-one + (1S,2S,5S,8R)-2-(benzylsulfanyl)-4,4,8-trimethyltricyclo[6.3.1.01,5]dodec-9-ene + (1S,2S,5S,8R,9R)-2,9-bis(benzylsulfanyl)-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecane

Conditions	Yield
With boron trifluoride diethyl etherate In chloroform for 5h; Reflux;	A 21% B 25% C 51%

caryophyllene oxide (1139-30-6) + 2-methylpropan-2-thiol (75-66-1) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + clovanediol (2649-64-1) + (1S,2S,5S,8R)-2-tert-butylsulfanyl-4,4,8-trimethyltricyclo[6.3.1.01,5]dodec-9-ene + (1S,2S,5S,8R,9R)-2,9-bistert-butylsulfanyl-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecane

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane Reflux;	A 10% B 7% C 35% D 48%

caryophyllene oxide (1139-30-6) + aniline (62-53-3) + acetonitrile (75-05-8) → 2β-phenylaminoclovan-9α-ol + N-(9α-hydroxyclovan-2β-yl)-N'-phenyl acetamidine

Conditions	Yield
With tin(II) trifluoromethanesulfonate at 80℃; for 24h;	A 5% B 47%

caryophyllene oxide (1139-30-6) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + 1R,5S,9S-11,11-dimethyl-4,8-bismethylenebicyclo<7.2.0>undecan-5-ol (19431-79-9) + isocaryolan-9-one

Conditions	Yield
With ethenetetracarbonitrile In dimethyl sulfoxide for 96h; Ambient temperature;	A 46% B 19% C 2%

caryophyllene oxide (1139-30-6) + phenylmethanethiol (100-53-8) → (1S,2S,5S,8R,9R)-2-(benzylsulfanyl)-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecan-9-ol + (1S,2S,6S,9R)-2-(benzylsulfanyl)-6,2,10,10-tetramethylbicyclo[7.2.0]undecan-5-one + (1S,2S,5R,9S)-7-(benzylsulfanyl)-1,4,4,8-tetramethyl-12-oxatricyclo[7.2.1.02,5]dodecane

Conditions	Yield
With boron trifluoride diethyl etherate In chloroform at 20℃; for 2h;	A 46% B 13% C 26%

caryophyllene oxide (1139-30-6) → (+)-(6R,7R)-6,7-epoxy-6,7-dihydro-β-farnesene

Conditions	Yield
at 550℃; under 0.5 Torr;	45%
at 550℃; under 0.1 - 2 Torr; for 0.000277778h; Product distribution; Thermodynamic data; flash vacuum thermolysis; further stereoisomers; variation of temperature; activation energy;	43%

caryophyllene oxide (1139-30-6) + phenylmethanethiol (100-53-8) → 4α,11,11-trimethyl-8-methylene-1β,9α-bicyclo[7.2.0]undecan-5-one (68263-68-3) + clovanediol (2649-64-1) + C15H24O + (1S,2S,5S,8R,9R)-2-(benzylsulfanyl)-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecan-9-ol

Conditions	Yield
With zinc(II) chloride In chloroform for 5h; Reflux;	A 12% B 26% C 10% D 45%

caryophyllene oxide (1139-30-6) + 2-methylpropan-2-thiol (75-66-1) → 4α,11,11-trimethyl-8-methylene-1β,9α-bicyclo[7.2.0]undecan-5-one (68263-68-3) + clovanediol (2649-64-1) + (1S,2S,5S,8R,9R)-2-tert-butylsulfanyl-4,4,8-trimethyltricyclo[6.3.1.01,5]dodecan-9-ol + 4,10,10-trimethyl-7-methylene-1β,8α-bicyclo[6.2.0]decene-4-carboxaldehyde (475285-25-7)

Conditions	Yield
With zinc(II) chloride In dichloromethane at 20℃; Catalytic behavior;	A 8% B 21% C 44% D 7%

caryophyllene oxide (1139-30-6) + 2-bromoethanol (540-51-2) → 2β-(2-bromoethoxy)clovan-9α-ol (357186-68-6)

Conditions	Yield
With ethenetetracarbonitrile at 25℃;	43%

methanol (67-56-1) + caryophyllene oxide (1139-30-6) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + 9α-hydroxy-2β-methoxyclovane (127156-29-0) + isocaryolan-9-one + (1S,5R,6R,9R)-6-Methoxy-10,10-dimethyl-2-methylene-bicyclo[7.2.0]undecan-5-ol

Conditions	Yield
With ethenetetracarbonitrile for 24h; Ambient temperature; Further byproducts given;	A 20% B 42% C 11% D 6%

methanol (67-56-1) + caryophyllene oxide (1139-30-6) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + 9α-hydroxy-2β-methoxyclovane (127156-29-0) + (Z)-(1R,5R,8R,9S)-8-Methoxy-4,8,11,11-tetramethyl-bicyclo[7.2.0]undec-3-en-5-ol + (1S,5R,6R,9R)-6-Methoxy-10,10-dimethyl-2-methylene-bicyclo[7.2.0]undecan-5-ol

Conditions	Yield
With ethenetetracarbonitrile for 24h; Ambient temperature; Further byproducts given;	A 20% B 42% C 3% D 6%

caryophyllene oxide (1139-30-6) → caryophylla-2(12),6(13)-dien-5β-ol (19431-76-6) + 9α-hydroxy-2β-methoxyclovane (127156-29-0) + isocaryolan-9-one + (1S,5R,6R,9R)-6-Methoxy-10,10-dimethyl-2-methylene-bicyclo[7.2.0]undecan-5-ol

Conditions	Yield
With ethenetetracarbonitrile In methanol for 24h; Ambient temperature; Further byproducts given;	A 20% B 42% C 11% D 6%

caryophyllene oxide (1139-30-6) + 4-methoxy-aniline (104-94-9) + acetonitrile (75-05-8) → 2β-(p-methoxyphenylamino)clovan-9α-ol + N-((3S,3aS,6R,7R,9aS)-6-Hydroxy-1,1,7-trimethyl-decahydro-3a,7-methano-cyclopentacycloocten-3-yl)-N'-(4-methoxy-phenyl)-acetamidine

Conditions	Yield
With tin(II) trifluoromethanesulfonate at 80℃; for 24h;	A 2% B 42%

caryophyllene oxide (1139-30-6) + acetonitrile (75-05-8) + 4-bromo-aniline (106-40-1) → N-(4-Bromo-phenyl)-N'-((3S,3aS,6R,7R,9aS)-6-hydroxy-1,1,7-trimethyl-decahydro-3a,7-methano-cyclopentacycloocten-3-yl)-acetamidine

Conditions	Yield
With tin(II) trifluoromethanesulfonate at 80℃; for 24h;	39%

Upstream product

• 87-44-5 β-caryophyllene 
• 3691-12-1 (1S,4S,7R)-7-Isopropenyl-1,4-dimethyl-1,2,3,4,5,6,7,8-octahydro-azulene 
• 93-59-4 Perbenzoic acid 
• 87-44-5 β-caryophyllene 
• 61824-50-8 (Z)-(1R,9S)-4,11,11-Trimethyl-8-methylene-bicyclo[7.2.0]undec-3-en-5-one 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 10306-22-6 (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.0^4,6]dodcan-9-one 
• 10577-25-0 5,6-epoxy-2-hydroxymethyl-6,10,10-trimethyl-bicyclo[7.2.0]undecan-2-ol 
• 2311-91-3 monoperoxyphthalic acid 
• 64-19-7 acetic acid 

Downstream Products

• 10306-22-6 (1R,4R,6R,10S)-4,12,12-trimethyl-5-oxatricyclo[8.2.0.0^4,6]dodcan-9-one 
• 2649-64-1 clovanediol 
• 155485-76-0 (β,9β)-caryolane-1,9-diol 
• 92760-17-3 (1R,5S,8R,9R)-4,4,8-trimethylbicyclo<6.3.1.0^1,5>dodeca-2-en-9-ol 
• 122571-87-3 (1R,2S,5R,8S,9S)-1,4,4,8-tetramethyltricyclo[6.3.0.0^2,5]undec-9-yl acetate 
• 86834-01-7 4,5-dihydrocaryophyllen-4β-ol 
• 92174-64-6 Acetic acid (1S,5S,6S,9R)-6,10,10-trimethyl-2-methylene-bicyclo[7.2.0]undec-5-yl ester 
• 92174-64-6 1R,4R,5S,9S-4,5-dihydrocaryophyllen-5-ol acetate 
• 99881-55-7 1R,5R,9S-5-acetoxy-11,11-dimethyl-4,8-bismethylenebicyclo<7.2.0>undecane 
• 87-44-5 β-caryophyllene 
• 88514-10-7 ((1S,8R)-4,10,10-Trimethyl-7-methylene-bicyclo[6.2.0]dec-4-yl)-methanol 
• 19431-76-6 caryophyllenol-I 
• 19431-79-9 (1S,5S,9R)-10,10-Dimethyl-2,6-dimethylene-bicyclo[7.2.0]undecan-5-ol 
• 62346-22-9 buddledin C 

Relevant articles and documents

PROCESS FOR PREPARING CARYOPHYLLENE OXIDE

The present invention relates to a method for oxidizing beta-caryophyllene with oxygen, in particular atmospheric oxygen, which avoids the use of catalysts, enzymes and solvents. Furthermore, the present invention provides a mixture comprising certain caryophyllene oxides as well as their use as a flavor and/or fragrance. The present invention also relates to products and semi-finished products comprising the mixture according to the invention.

An ultrathin amino-acid based copper(II) coordination polymer nanosheet for efficient epoxidation of β-caryophyllene

Natural amino acids are important building blocks for the construction of intriguing coordination polymers (CPs) because of their abundance, inexpensiveness and environmental benignness. Herein, two copper(II) CPs, namely, 2D CuIle-e nanosheet (e: ethanol) and 1D CuIle-m nanoshuttle (m: methanol), were fabricated from L-isoleucine (Ile) and well characterized with single-crystal x-ray diffraction, XPS spectra, TEM and AFM, etc. More importantly, two novel and stable catalytic nanosystems, i.e. CuIle-e/acetone/TBHP (tert-butyl hydroperoxide) and CuIle-e/THF/O2/TBHP, were thus conveniently built by using ultrathin 2D CuIle-e nanosheet (~ 2.3 nm) in suitable aprotic solvents. Under mild conditions, complete conversion of β-caryophyllene and good yields (86.1% or 87.2%) for β-caryophyllene epoxide were gained via CuIle-e/acetone/TBHP or CuIle-e/THF/O2 (1 atm)/TBHP (10.0 mol%), respectively. Notably, ultrathin CuIle-e nanosheet showed fairly satisfactory stability, which may open a unique window for the facile fabrication of new amino-acid based CP nanosystems with outstanding catalytic performances in actual applications.

Tailoring chemoenzymatic oxidation: Via in situ peracids

Epoxidation chemistry often suffers from the challenging handling of peracids and thus requires in situ preparation. Here, we describe a two-phase enzymatic system that allows the effective generation of peracids and directly translate their activity to the epoxidation of olefins. We demonstrate the approach by application to lipid and olefin epoxidation as well as sulfide oxidation. These methods offer useful applications to synthetic modifications and scalable green processes.