21947-87-5

Basic information

• Product Name: Diisopinocampheylborane
• Synonyms: Bis[(1S,2R,3S,5S)-2,6,6-trimethylbicyclo[3.1.1]hept-3-yl]borane;(+)-Diisopinocampheylborane;Diisopinocampheylborane;Borane,bis[(1S,2R,3S,5S)-2,6,6-triMethylbicyclo[3.1.1]hept-3-yl]-;Bis((1S,2R,3S,5S)-2,6,6-trimethylbicyclo[3.1.1]heptan-3-yl)borane
• CAS NO: 21947-87-5
• Molecular Formula: C₂₀H₃₅B
• Molecular Weight: 286.3
• Mol File: 21947-87-5.mol
• Article Data: 12

Chemical Properties

• Boiling Point: 351.475oC at 760 mmHg
• Flash Point: 166.367oC
• Appearance: /
• Vapor Pressure: 0mmHg at 25°C
• Storage Temp.: Hygroscopic, Refrigerator, under inert atmosphere
• Solubility: Dichloromethane (Slightly), THF (Slightly)
• Stability: Extremely Moisture Sensitive
• CAS DataBase Reference: Diisopinocampheylborane(CAS DataBase Reference)
• NIST Chemistry Reference: Diisopinocampheylborane(21947-87-5)
• EPA Substance Registry System: Diisopinocampheylborane(21947-87-5)

Safety Data

• Hazardous Substances Data: 21947-87-5(Hazardous Substances Data)

Usage

Chemical Properties

White Sticky Solid

Uses

Diisopinocampheylborane is a hydroborane with many applications in organic synthesis of nicotine analogs, (-)-Invictolide, (+)-strictifolione and other organic compounds.

InChI:InChI=1/C20H35B/c1-11-15-7-13(19(15,3)4)9-17(11)21-18-10-14-8-16(12(18)2)20(14,5)6/h11-18,21H,7-10H2,1-6H3

Synthetic route

(-)-α-pinene (7785-26-4) → L-diisopinocampheylborane (21947-87-5)

Conditions	Yield
With borane N-ethyl-N-isopropylaniline complex In 1,4-dioxane hydroboration;	99%
With dimethylsulfide borane complex In tetrahydrofuran at 20℃; Inert atmosphere;	73%
With sodium tetrahydroborate; boron trifluoride diethyl etherate

(-)-α-pinene (7785-26-4) + dimethylsulfide borane complex (13292-87-0) → L-diisopinocampheylborane (21947-87-5)

Conditions	Yield
In tetrahydrofuran at 20℃; for 16h; Inert atmosphere;	82%
In tetrahydrofuran at 0℃; for 0.5h;	60%
In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere;	52%
In tetrahydrofuran
In tetrahydrofuran at 0℃;

dimethylsulfide borane complex (13292-87-0) + (1R,5R)-(+)-β-pinene (127-91-3) → L-diisopinocampheylborane (21947-87-5)

Conditions	Yield
In tetrahydrofuran pinene was slowly added to THF soln. of BMS at 0°C (N2); stirring for 2.5 h; evapn.;

borane-THF (14044-65-6) + (-)-α-pinene (7785-26-4) → L-diisopinocampheylborane (21947-87-5)

Conditions	Yield
In tetrahydrofuran at 0 - 20℃; for 2h; Inert atmosphere; stereoselective reaction;

1-benzyl-3-methyl-1H-imidazol-3-ium iodide (15095-61-1) + L-diisopinocampheylborane (21947-87-5) → (1-benzyl-3-methylimidazol-2-yl)di((1S,2R,3S,5S)-isopinocampheyl)borane

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran at 25℃; Inert atmosphere; Schlenk technique;	83%

benzaldehyde (100-52-7) + L-diisopinocampheylborane (21947-87-5) + 3-phenyl-1-(tributylstannyl)-1,2-propadiene (155818-57-8) → C6H5CH(OH)CH(C6H5)CHCHSn(C4H9)3

Conditions	Yield
In diethyl ether Sn compd. in Et2O treated with B compd. at 0°C for 5 h, C6H5CHO added at -78°C, stirred at -78°C for 8 h; NaHCO3 and H2O2 added at 0°C; 94 % ee;	76%

3-phenyl-propionaldehyde (104-53-0) + L-diisopinocampheylborane (21947-87-5) + 3-phenyl-1-(tributylstannyl)-1,2-propadiene (155818-57-8) → C6H5(CH2)2CH(OH)CH(C6H5)CHCHSn(C4H9)3

Conditions	Yield
In diethyl ether Sn compd. in Et2O treated with B compd. at 0°C for 5 h, C6H5(CH2)2CHO added at -78°C, stirred at -78°C for 8 h; NaHCO3 and H2O2 added at 0°C; 94 % ee;	71%

L-diisopinocampheylborane (21947-87-5) + 1-methyl-3-tert-butylimidazolium halide → (1-tert-butyl-3-methylimidazol-2-yl)di((1S,2R,3S,5S)-isopinocampheyl)borane

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran at 25℃; Inert atmosphere; Schlenk technique;	60%

N-methyl-N'-phenyl imidazolium iodide (65039-06-7) + L-diisopinocampheylborane (21947-87-5) → (1-methyl-3-phenylimidazol-2-yl)di((1S,2R,3S,5S)-isopinocampheyl)borane

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran at 25℃; Inert atmosphere; Schlenk technique;	56%

1,3-dimethylimidazolim iodide (4333-62-4) + L-diisopinocampheylborane (21947-87-5) → 1,3-dimethylimidazol-2-ylidene-di-(1S,2R,3S,5S)-isopinocampheylborane

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran at 20℃; for 20h; Sealed tube; Inert atmosphere; Glovebox;	37%
With potassium hexamethylsilazane In tetrahydrofuran at 25℃; for 20h; Inert atmosphere; Schlenk technique;	37%

L-diisopinocampheylborane (21947-87-5) + 1,3-diisopropyl-1H-imidazol-3-ium chloride → 1,3-diisopropylimidazol-2-ylidene-di-(1S,2R,3S,5S)-isopinocampheylborane

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran at 20℃; for 20h; Sealed tube; Inert atmosphere; Glovebox;	34%

L-diisopinocampheylborane (21947-87-5) + 1,3-diisopropylimidazolium halide → 1,3-diisopropylimidazol-2-ylidene-di-(1S,2R,3S,5S)-isopinocampheylborane

Conditions	Yield
With potassium hexamethylsilazane In tetrahydrofuran at 25℃; Inert atmosphere; Schlenk technique;	34%

3-methoxy-2,5-dihydro-furan (22929-50-6) + L-diisopinocampheylborane (21947-87-5) → ((3R,4S)-4-Methoxy-tetrahydro-furan-3-yl)-bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-borane + ((3S,4R)-4-Methoxy-tetrahydro-furan-3-yl)-bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-borane

Conditions	Yield
With Pinene In tetrahydrofuran at -25℃; for 30h; asymmetric hydroboration; Title compound not separated from byproducts;

1-methoxycyclopentene (1072-59-9) + L-diisopinocampheylborane (21947-87-5) → ((1R,2R)-2-Methoxy-cyclopentyl)-bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-borane + ((1S,2S)-2-Methoxy-cyclopentyl)-bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-borane

Conditions	Yield
With Pinene In tetrahydrofuran at -25℃; for 76h; asymmetric hydroboration; Title compound not separated from byproducts;

1-ethoxycyclopentene (17065-24-6) + L-diisopinocampheylborane (21947-87-5) → ((1R,2R)-2-Ethoxy-cyclopentyl)-bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-borane + ((1S,2S)-2-Ethoxy-cyclopentyl)-bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-borane

Conditions	Yield
With Pinene In tetrahydrofuran at -25℃; for 80h; asymmetric hydroboration; Title compound not separated from byproducts;

1-(benzyloxy)cyclopentene (113548-17-7) + L-diisopinocampheylborane (21947-87-5) → ((1R,2R)-2-Benzyloxy-cyclopentyl)-bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-borane + ((1S,2S)-2-Benzyloxy-cyclopentyl)-bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-borane

Conditions	Yield
With Pinene In tetrahydrofuran at -15℃; for 120h; asymmetric hydroboration; Title compound not separated from byproducts;

L-diisopinocampheylborane (21947-87-5) + 9-(cyclopent-1-enyloxy)-9-bora-bicyclo[3.3.1]nonane → 9-{(1R,2R)-2-[Bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-boranyl]-cyclopentyloxy}-9-bora-bicyclo[3.3.1]nonane + 9-{(1S,2S)-2-[Bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-boranyl]-cyclopentyloxy}-9-bora-bicyclo[3.3.1]nonane

Conditions	Yield
With Pinene In tetrahydrofuran at -10℃; for 72h; asymmetric hydroboration; Title compound not separated from byproducts;

L-diisopinocampheylborane (21947-87-5) + 2-allenyl-4,4,5,5-tetraphenyl-1,3,2-dioxaborolane (479579-58-3) → 2-{(E)-3-[Bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-boranyl]-propenyl}-4,4,5,5-tetraphenyl-[1,3,2]dioxaborolane

Conditions	Yield
In dichloromethane at 0℃; for 2.5h;
In dichloromethane at 0 - 23℃;

L-diisopinocampheylborane (21947-87-5) + 2-allenyl-[1,3,2]-dioxaborinane (169517-16-2) → 2-{(E)-3-[Bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-boranyl]-propenyl}-[1,3,2]dioxaborinane

Conditions	Yield
In dichloromethane at 0 - 20℃;

L-diisopinocampheylborane (21947-87-5) + 2-allenyl-4,4,5,5-tetraphenyl-1,3,2-dioxaborolane (479579-58-3) → 2-{(E)-3-[Bis-((1S,2R,3S,5S)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl)-boranyl]-allyl}-4,4,5,5-tetraphenyl-[1,3,2]dioxaborolane

Conditions	Yield
In dichloromethane at 0℃; for 2h;

methanol (67-56-1) + L-diisopinocampheylborane (21947-87-5) → (+)-B-methoxydiisocamphenylborane (99438-28-5)

Conditions	Yield
In diethyl ether at 0℃; for 2h;
In tetrahydrofuran at 20℃; for 4h; Inert atmosphere;

(R)-1-methoxy-4-((pent-4-yn-2-yloxy)methyl)benzene (603040-81-9) + L-diisopinocampheylborane (21947-87-5) → C33H51BO2

Conditions	Yield
In tetrahydrofuran at -35 - 20℃; for 2.5h;

L-diisopinocampheylborane (21947-87-5) → B-allyldiisopinocampheylborane (106356-53-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: diethyl ether / 2 h / 0 °C 2: diethyl ether / 1 h / 20 °C View Scheme

L-diisopinocampheylborane (21947-87-5) → C72H88B2O6Si

Conditions	Yield
Multi-step reaction with 2 steps 1: CH2Cl2 / 2 h / 0 °C 2: CH2Cl2 / 18 h / -78 °C View Scheme

L-diisopinocampheylborane (21947-87-5) → C85H100B2O8Si

Conditions	Yield
Multi-step reaction with 2 steps 1: CH2Cl2 / 2 h / 0 °C 2: CH2Cl2 / 2.5 h / -78 °C View Scheme

norborn-2-ene (498-66-8) + L-diisopinocampheylborane (21947-87-5) → exo-norbornyldiisopinocampheylborane

Conditions	Yield
Norbornene is hydroborated with Ipc2BH at -25°C (83% ee).;

L-diisopinocampheylborane (21947-87-5) → B-bromodiisopinocampheylborane (175892-48-5)

Conditions	Yield
With hydrogen bromide In pentane 0°C;;

L-diisopinocampheylborane (21947-87-5) → B-iododiisopinocampheylborane (175892-49-6)

Conditions	Yield
With iodine In pentane 0°C;;

L-diisopinocampheylborane (21947-87-5) → B-chlorodiisopinocampheylborane (112246-73-8)

Conditions	Yield
With hydrogenchloride In pentane 0°C;;

(Z)-2-Butene (590-18-1) + L-diisopinocampheylborane (21947-87-5) → B(OH)2CHCH3C2H5 (82248-43-9)

Conditions	Yield
With sodium hydroxide; acetaldehyde In tetrahydrofuran mixt. of B compd. and pinene was kept at 0°C (N2) for 3 d; cooling to -25°C, addn. of cis-butene; stirring for 6 h; treatment with AcH with stirring at 25°C for 36 h, evapn., addn. of pentane, treatment with aq. NaOH; treatment with aq. HCl, extn. with Et2O, drying in vac.;

Upstream product

• 7785-26-4 (-)-α-pinene 
• 13292-87-0 dimethylsulfide borane complex 
• 127-91-3 (1R,5R)-(+)-β-pinene 
• 14044-65-6 borane-THF 

Downstream Products

• 1428744-69-7 (S)-E-α-phenyldimethylsilyl(d-diisopinocampheyl)-crotylborane 
• 1196-00-5 (+)-isopinocampheol 

Relevant articles and documents

Synthetic studies on callipeltin A: Stereoselective synthesis of (2 R,3 R,4 S)-3-hydroxy-2,4,6-trimethylheptanoic acid

Asymmetric synthesis of (2R,3R,4S)-3-hydroxy-2,4,6-trimethylheptanoic acid, the -hydroxy acid unit that acylates the N-terminus of cyclic depsipeptide callipeltin A, has been devised. The approach involves the desymmetrization of a bicyclic precursor, which generates the three chiral centers

Preparation of crystalline (diisopinocampheyl)borane

-

Stereospecific Pd-catalyzed cross-coupling reactions of secondary alkylboron nucleophiles and aryl chlorides

We report the development of a Pd-catalyzed process for the stereospecific cross-coupling of unactivated secondary alkylboron nucleophiles and aryl chlorides. This process tolerates the use of secondary alkylboronic acids and secondary alkyltrifluoroborates and occurs without significant isomerization of the alkyl nucelophile. Optically active secondary alkyltrifluoroborate reagents undergo cross-coupling reactions with stereospecific inversion of configuration using this method.