280-64-8

Usage

Uses

Used in Synthetic Organic Chemistry:
9-Borabicyclo[3.3.1]nonane is used as a selective hydroboration reagent for the region-selective addition of alkenes, followed by oxidative cleavage using hydrogen peroxide. This process is crucial in the synthesis of various organic compounds.
Used in Suzuki Reactions:
In the field of cross-coupling reactions, 9-BBN is employed in Suzuki reactions, which are widely used for the formation of carbon-carbon bonds, particularly in the synthesis of complex organic molecules.
Used as a Protecting Group for Alkenes:
9-Borabicyclo[3.3.1]nonane acts as a protecting group for alkenes, preventing unwanted reactions and ensuring the selective formation of desired products.
Used in Copper-Catalyzed Cross-Coupling Reactions:
9-BBN is utilized in copper-catalyzed cross-coupling reactions of organoboron compounds with primary alkyl halides and pseudohalides, further expanding its applications in synthetic organic chemistry.
Used in Hetero-Diels-Alder Reaction:
9-Borabicyclo[3.3.1]nonane is used as a reactant in the Hetero-Diels-Alder reaction, which is essential for the synthesis of spirocyclic alkaloids, a class of biologically active compounds.
Used in Intramolecular Insertion of Alkenes:
9-BBN is employed in the intramolecular insertion of alkenes into palladium-nitrogen bonds, a key step in the synthesis of various complex organic molecules.
Used in Linear SPPS Synthesis of Ubiquitin Derivatives:
In the field of peptide synthesis, 9-BBN is used in the linear solid-phase peptide synthesis (SPPS) of ubiquitin derivatives, which are important for studying the functions and interactions of ubiquitin in cellular processes.
Used in Preparation of (Phosphonoacetyl)ornithine:
9-Borabicyclo[3.3.1]nonane is used in the preparation of (phosphonoacetyl)ornithine, a compound used to study the effects on arginine biosynthetic genes in yeast, providing insights into the regulation of arginine metabolism.

Purification Methods

It is available as the solid dimer or in tetrahydrofuran solution. The solid is relatively stable and can be purified by distillation in a vacuum (as dimer) and by recrystallisation from tetrahydrofuran (solubility at room temperature is 9.5%, 0.78M), filter off the solid under N2, wash it with dry pentane and dry it in vacuo at ca 100o. The solid is a dimer (IR 1567cm-1), stable in air (for ca 2 months), and can be heated for 24hours at 200o in an inert atmosphere without loss of hydride activity. It is a dimer in tetrahydrofuran solution also (IR 1567cm-1). It is sensitive to H2O and air (O2) in solution. Its concentration in solution can be determined by reaction with MeOH and measuring the volume of H2 liberated, or it can be oxidised to cis-cyclooctane-1,5-diol (m 73.5-74.5o). [IR: Knights & Brown J Am Chem Soc 90 5280 1968, Brown et al. J Am Chem Soc 96 7765 1974, Brown et al. J Org Chem 41 1778 1976, Brown & Chen J Org Chem 46 3978 1981, Fieser & Fieser Reagents for Org Synth 2 31, 3 24, 10 48, 15 43, 17, 49.] Borane pyridine complex [110 -51 -0] M 92.9, m 8-10o, 10-11o, b 86o/7mm, 100-1 0 1o/12mm, d 4 0.785. Dissolve it in Et2O and wash it with H2O in which it is insoluble. Evaporate the Et2O and distil the residual oil to gives better than 99.8% purity. Its vapour pressure is less than 0.1mm at room temperature. [Taylor et al. J Am Chem Soc 77 1506 1955, Beilstein 20 IV 2235.]

InChI:InChI=1/C8H14B/c1-3-7-5-2-6-8(4-1)9-7/h7-8H,1-6H2

Synthetic route

1,5-cis,cis-cyclooctadiene (1552-12-1, 111-78-4) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
With borane N-ethyl-N-isopropylaniline complex In 1,4-dioxane hydroboration; Heating;	87%
With dimethylsulfide borane complex In tetrahydrofuran at -5 - 67℃; for 1.75h;

borane-THF (14044-65-6) + 9-(di-tert-butylphosphanyl)-9-bora{3.3.1}bicyclononane (149468-33-7) → μ-(di-tert-butylphosphanyl)-diborane (149075-30-9) + 1,1,3,3-tetra-tert-butyl-1,3,2,4-diphosphadiboracyclobutane (149075-28-5) + μ-(di-tert-butylphosphanyl)-di-9-bora{3.3.1}bicyclononane (149075-29-6) + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In tetrahydrofuran dropping soln. of BH3*THF in THF to soln. of borane in THF at -78°C, under N2 or Ar; refluxing for 1 h; mechansim discussed;; removal of solvent in vac.; recrystn. from ether; 1. and 2. fraction product mixts., 3. fraction pure 9-borabicyclo(3.3.1)nonane, 4. fraction small amt. of pure (BH2P(tert-butyl)2)2; detn. by NMR;;	A n/a B n/a C n/a D 75%

((CH3)2CH)2NCH2CH(CH3)2*BH3 + 1,5-dicyclooctadiene (5259-72-3, 10060-40-9, 111-78-4) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In 1,4-dioxane N2-atmosphere; dropwise cyclooctadiene addn. (20°C, stirring), stirring (room temp, 3 h, refluxing , 2 h); crystn. (room temp.), decanting, washing (n-pentane), drying (reduced pressure), recrystn. (THF);	70%

1,5-cis,cis-cyclooctadiene (1552-12-1, 111-78-4) → 9-BBN (38895-05-5) + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
With borane N-ethyl-N-isopropylaniline complex In 1,4-dioxane at 20℃; for 1h; hydroboration; Title compound not separated from byproducts;

9-chloro-9-borabicyclo{3.3.1}nonane (22086-34-6) + 1-lithio-2,4,6-trimethylborazine → 9-N3B3H2(CH3)3-9-borabicyclo [2.2.1]nonane + 9-methyl-9-borabicyclo[3.3.1]nonane (23418-81-7) + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In diethyl ether; toluene Title compound not separated from byproducts.;

9-borabicyclo[3.3.1]nonane dimer (21205-91-4) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
With acetophenone In tetrahydrofuran Kinetics; 25°C; detected by IR;
With pivalaldehyde In tetrahydrofuran Kinetics; 25°C; detected by IR;
With 2,4-dimethylpentan-3-one In tetrahydrofuran Kinetics; 25°C; detected by IR;

C8H14BBrS(CH3)2 (70160-59-7) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
With Li(t-BuO)3AlH In tetrahydrofuran byproducts: B-alkoxy-9-borabicyclo-[3.3.1]nonane; 0°C, 0.25 h; detected by 11B NMR;
With LiAlH4 In tetrahydrofuran byproducts: AlBr3, LiBr; 0.25 equivalent LiAlH4, 0°C, 0.25 h; detected by 11B NMR;

lithium borohydride + C8H14BBrS(CH3)2 (70160-59-7) → dimethylsulfide borane complex (13292-87-0) + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In tetrahydrofuran byproducts: LiBr; 0°C, 0.25 h; detected by 11B NMR;

potassium tri(isopropoxy)borohydride + C8H14BBrS(CH3)2 (70160-59-7) → Triisopropyl borate (5419-55-6) + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In tetrahydrofuran byproducts: B-alkoxy-9-borabicyclo[3.3.1]nonane, KBr; 1 equivalent K(i-PrO)3BH, 25°C, 8.0 h; detected by 11B NMR;
In tetrahydrofuran byproducts: B-alkoxy-9-borabicyclo[3.3.1]nonane, KBr; 1 equivalent K(i-PrO)3BH, 0°C, 0.25 h; detected by 11B NMR;

lithium-9-borabicyclo[3.3.1]nonane hydride + C8H14BBrS(CH3)2 (70160-59-7) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In tetrahydrofuran 0°C, 0.25 h; detected by 11B NMR;

C8H14BClS(CH3)2 (70160-58-6) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
With Li(CH3O)3AlH In tetrahydrofuran byproducts: B-alkoxy-9-borabicyclo[3.3.1]nonane; 0°C, 0.25 h; detected by 11B NMR;
With LiAlH4 In tetrahydrofuran byproducts: AlCl3, LiCl; 0.25 equivalent LiAlH4, 0°C, 0.25 h; detected by 11B NMR;

C8H14BClS(CH3)2 (70160-58-6) + lithium triethylborohydride (22560-16-3) → lithium-9-borabicyclo[3.3.1]nonane hydride + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In tetrahydrofuran byproducts: B-alkoxy-9-borabicyclo[3.3.1]nonane, (C2H5)3B; 0°C, 0.25 h; detected by 11B NMR;

lithium borohydride + C8H14BClS(CH3)2 (70160-58-6) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In tetrahydrofuran byproducts: LiCl, BH3S(CH3)2; 0°C, 0.25 h; detected by 11B NMR;

sodium tetrahydroborate (16940-66-2) + C8H14BClS(CH3)2 (70160-58-6) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In diethylene glycol dimethyl ether byproducts: NaCl, BH3S(CH3)2; 25°C, 0.25 h; detected by 11B NMR;

potassium tri(isopropoxy)borohydride + C8H14BClS(CH3)2 (70160-58-6) → Triisopropyl borate (5419-55-6) + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In tetrahydrofuran byproducts: B-alkoxy-9-borabicyclo-[3.3.1]nonane, KCl; 1 equivalent K(i-PrO)3BH, 0°C, 0.25 h; detected by 11B NMR;

lithium-9-borabicyclo[3.3.1]nonane hydride + C8H14BClS(CH3)2 (70160-58-6) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In tetrahydrofuran 0°C, 0.25 h; detected by 11B NMR;

tetrakis(dimethylamido)zirconium (IV) (19756-04-8) + [C8BH14]2C10H6(NH)2 (187403-06-1) → C8BH14C10H6(NH)2Zr[N(CH3)2]3 + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In not given byproducts: (CH3)2N;

tetrakis(dimethylamido)titanium(IV) + [C8BH14]2C10H6(NH)2 (187403-06-1) → C8BH14C10H6(NH)2Ti[N(CH3)2]3 + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In not given byproducts: (CH3)2N;

dimethylsulfide borane complex (13292-87-0) + 1,5-dicyclooctadiene (5259-72-3, 10060-40-9, 111-78-4) → 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In 1,2-dimethoxyethane at 20 - 60℃;

C26H47BNiO2P2 (1378876-25-5) → (iPrPOCOP)NiH (1108747-39-2) + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In (2)H8-toluene at 22℃; Equilibrium constant;

9-borabicyclo[3.3.1]nonane dimer (21205-91-4) + fluorocyclohexane (372-46-3) → B-cyclohexyl-9-borabicyclo<3.3.1>nonane (53535-83-4) + 9-fluoro-9-boracyclo{3.3.1}nonane (22086-35-7) + 9-bora-bicyclo[3.3.1]nonane (280-64-8)

Conditions	Yield
In dichloromethane-d2 for 24h; Inert atmosphere; Glovebox; Sealed tube;

1,5-Hexadien (592-42-7) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 9,9'-hexane-1,6-diyl-bis-9-bora-bicyclo[3.3.1]nonane (88703-69-9)

Conditions	Yield
In tetrahydrofuran at 40℃; for 24h; Schlenk technique; Inert atmosphere;	100%
In tetrahydrofuran at 20℃; for 3h; Addition;
In tetrahydrofuran at 20℃; for 4.5h; Addition; Hydroboration;
In tetrahydrofuran at 20℃; for 3h;

9-bora-bicyclo[3.3.1]nonane (280-64-8) + 2-amino-1-benzylamine (4403-69-4) → (2-aminomethyl-phenyl)-(9-bora-bicyclo[3.3.1]non-9-yl)-amine

Conditions	Yield
In tetrahydrofuran at 20℃;	100%
In tetrahydrofuran; hexane Yield given;

9-bora-bicyclo[3.3.1]nonane (280-64-8) → C8H15B*H(1-)*K(1+)

Conditions	Yield
With KH activated aith LiAlH4 In tetrahydrofuran at 25℃; for 0.5h;	100%

2-Aminobenzyl alcohol (5344-90-1) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C15H21BNO(1-)*H(1+)

Conditions	Yield
In tetrahydrofuran; hexane at 20℃;	100%

2-Hydroxybenzylamine (932-30-9) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C15H21BNO(1-)*H(1+)

Conditions	Yield
In tetrahydrofuran; hexane at 20℃;	100%

9-bora-bicyclo[3.3.1]nonane (280-64-8) + propan-1-ol-3-amine (156-87-6) → C11H21BNO(1-)*H(1+)

Conditions	Yield
In tetrahydrofuran; hexane at 20℃;	100%

1-hexene (592-41-6) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 9-hexyl-9-borabicyclo[3.3.1]nonane (42371-64-2)

Conditions	Yield
In tetrahydrofuran at 60℃; for 12h; Schlenk technique; Inert atmosphere;	100%
In tetrahydrofuran at 25℃; for 24h; Schlenk technique; Inert atmosphere;	100%
In tetrahydrofuran at 20℃; for 2h;	87%

2,5-diallylpyrrole (42159-33-1) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 2,5-bis-[3'-(9''-borabicyclo[3.3.1]nonyl)propyl]pyrrole (206867-77-8)

Conditions	Yield
In tetrahydrofuran N2-atmosphere; dropwise addn. of 2 equiv. of B-compd. to pyrrole derivative, stirring (room temp., 15 h); solvent removal (vac.), distn.;	100%

7a-aza-7,7-dimethyl-6,7-dihydro-7-stanna-7aH-indene (191797-28-1) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → N-borabicyclo[3.3.1]nonyl-2(prop-(Z)-1-enyl-3'-dimethylstannyl)pyrrole (191797-33-8)

Conditions	Yield
In tetrahydrofuran N2-atmosphere; stirring equimolar amts. (room temp., 15 h); solvent removal;	100%

ethynyl[dimethyl(vinyl)silylethynyl]dimethylsilane (1236226-20-2) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 4-(9-borabicyclo[3.3.1]non-9-yl)-1,1,6,6-tetramethyl-1H,2H,3H,6H-1,6-disilapentalene (1236226-31-5)

Conditions	Yield
at 90 - 110℃; Inert atmosphere; regioselective reaction;	100%
In toluene (Ar), soln. of silane in toluene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);
In benzene (Ar), soln. of silane in benzene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);

1-(3-dimethylamino)propynyl[dimethyl(vinyl)silylethynyl]dimethylsilane (1236226-22-4) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 4-(9-borabicyclo[3.3.1]non-9-yl)-5-[(dimethylamino)methyl]-1,1,6,6-tetramethyl-1H,2H,3H,6H-1,6-disilapentalene (1236226-33-7)

Conditions	Yield
at 90 - 110℃; Inert atmosphere; regioselective reaction;	100%
In toluene (Ar), soln. of silane in toluene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.); elem. anal.;
In benzene (Ar), soln. of silane in benzene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.); elem. anal.;

dimethyl(vinyl)silylethynyl(phenylethynyl)dimethylsilane (1236226-21-3) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 4-(9-borabicyclo[3.3.1]non-9-yl)-1,1,6,6-tetramethyl-5-phenyl-1H,2H,3H,6H-1,6-disilapentalene (1236226-32-6)

Conditions	Yield
at 90 - 110℃; Inert atmosphere; regioselective reaction;	100%
In toluene (Ar), soln. of silane in toluene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);
In benzene (Ar), soln. of silane in benzene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);

(dimethyl(vinyl)silylethynyl)(dimethysilylethynyl)dimethylsilane (1236226-23-5) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 4-(9-borabicyclo[3.3.1]non-9-yl)-5-(dimethylsilyl)-1,1,6,6-tetramethyl-1H,2H,3H,6H-1,6-disilapentalene (1236226-34-8)

Conditions	Yield
at 90 - 110℃; Inert atmosphere; regioselective reaction;	100%
In toluene (Ar), soln. of silane in toluene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);
In benzene (Ar), soln. of silane in benzene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);

bromodimethylsilylethynyl[dimethyl(vinyl)silylethynyl]dimethylsilane (1236226-24-6) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 4-(9-borabicyclo[3.3.1]non-9-yl)-5-(bromodimethylsilyl)-1,1,6,6-tetramethyl-1H,2H,3H,6H-1,6-disilapentalene (1236226-35-9)

Conditions	Yield
at 90 - 110℃; Inert atmosphere; regioselective reaction;	100%
In toluene (Ar), soln. of silane in toluene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);
In benzene (Ar), soln. of silane in benzene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);

trimethylsilylethynyl[methyl(phenyl)(vinyl)silylethynyl]dimethylsilane (1236226-26-8) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 4-(9-borabicyclo[3.3.1]non-9-yl)-1,6,6-trimethyl-1-phenyl-5-(trimethylsilyl)-1H,2H,3H,6H-1,6-disilapentalene (1236226-37-1)

Conditions	Yield
at 90 - 110℃; Inert atmosphere; regioselective reaction;	100%
In toluene (Ar), soln. of silane in toluene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);
In benzene (Ar), soln. of silane in benzene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);

bromodimethylsilylethynyl[diphenyl(vinyl)silylethynyl]dimethylsilane (1236226-25-7) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 4-(9-borabicyclo[3.3.1]non-9-yl)-5-(bromodimethylsilyl)-6,6-dimethyl-1,1-diphenyl-1H,2H,3H,6H-1,6-disilapentalene (1236226-36-0)

Conditions	Yield
at 90 - 110℃; Inert atmosphere; regioselective reaction;	100%
In toluene (Ar), soln. of silane in toluene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);
In benzene (Ar), soln. of silane in benzene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);

triphenylsilylethynyl[methyl(phenyl)(vinyl)silylethynyl]dimethylsilane (1236226-27-9) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 4-(9-borabicyclo[3.3.1]non-9-yl)-1,6,6-trimethyl-1-phenyl-5-(triphenylsilyl)-1H,2H,3H,6H-1,6-disilapentalene (1236226-38-2)

Conditions	Yield
at 90 - 110℃; Inert atmosphere; regioselective reaction;	100%
In toluene (Ar), soln. of silane in toluene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);
In benzene (Ar), soln. of silane in benzene treated with equimolar amounts of 9-borabicyclo(3.3.1)nonane in one portion, heated up to 90-110°C for 2-5 min; evapd.(vac.);

dmap (1122-58-3) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C15H25BN2 (1283232-82-5)

Conditions	Yield
In dichloromethane at 20℃; Inert atmosphere;	100%

(4R)-5-(tert-butyldiphenylsilyloxy)-4-methyl-1-pentene (144693-95-8) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C30H45BOSi

Conditions	Yield
In tetrahydrofuran at 20℃; Inert atmosphere;	100%

C23H39BSi (1578266-74-6) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C31H54B2Si (1578266-79-1)

Conditions	Yield
In benzene-d6 at 80 - 100℃; for 0.666667h; Inert atmosphere;	100%

carbon dioxide (124-38-9) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 9-methoxy-9-BBN (38050-71-4)

Conditions	Yield
With 1,3-di-tert-butylimidazol-2-ylidene In tetrahydrofuran at 70℃; under 750.075 - 2250.23 Torr; for 0.2h; Solvent; Temperature; Reagent/catalyst; Inert atmosphere; Glovebox; Sealed tube;	100%
With 1-dimesitylboryl-1’-diphenylphosphino-ferrocene In tetrahydrofuran-d8 at 70℃; under 750.075 Torr; for 20h; Catalytic behavior; Reagent/catalyst; Temperature; Time; Inert atmosphere; Schlenk technique; Sealed tube;
With C9H18ClN3Si In tetrahydrofuran at 20℃; under 760.051 Torr; for 23h; Catalytic behavior; Mechanism; Reagent/catalyst; Time; Solvent;	100 %Spectr.

trimethylamine-N-oxide (1184-78-7) + 4-methyl-N-(2-propenyl)benzenesulfonamide (50487-71-3) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → N-(3-((1s,5s)-9-oxa-10-borabicyclo[3.3.2]decan-10-yl)propyl)-4-methylbenzenesulfonamide

Conditions	Yield
Stage #1: 4-methyl-N-(2-propenyl)benzenesulfonamide; 9-bora-bicyclo[3.3.1]nonane In tetrahydrofuran at 0 - 20℃; Stage #2: trimethylamine-N-oxide In tetrahydrofuran; dichloromethane	100%

trimethylamine-N-oxide (1184-78-7) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) + cyclohexene (110-83-8) → (1s,5s)-10-cyclohexyl-9-oxa-10-borabicyclo[3.3.2]decane

Conditions	Yield
Stage #1: 9-bora-bicyclo[3.3.1]nonane; cyclohexene In tetrahydrofuran at 0 - 20℃; Stage #2: trimethylamine-N-oxide In tetrahydrofuran; dichloromethane	100%

trimethylamine-N-oxide (1184-78-7) + 4-(allyloxy)-1-benzylpiperidine + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → 4-(3-((1s,5s)-9-oxa-10-borabicyclo[3.3.2]decan-10-yl)propoxy)-1-benzylpiperidine

Conditions	Yield
Stage #1: 4-(allyloxy)-1-benzylpiperidine; 9-bora-bicyclo[3.3.1]nonane In tetrahydrofuran at 0 - 20℃; Stage #2: trimethylamine-N-oxide In tetrahydrofuran; dichloromethane	100%

trimethylamine-N-oxide (1184-78-7) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) + 1-allyl-1H-pyrrolo[2,3-b]pyridine → 1-(3-((1s,5s)-9-oxa-10-borabicyclo[3.3.2]decan-10-yl)propyl)-1H-pyrrolo[2,3-b]pyridine

Conditions	Yield
Stage #1: 9-bora-bicyclo[3.3.1]nonane; 1-allyl-1H-pyrrolo[2,3-b]pyridine In tetrahydrofuran at 0 - 20℃; Stage #2: trimethylamine-N-oxide In tetrahydrofuran; dichloromethane	100%

C17H19N5(2+)*2C24H20B(1-) + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C33H49B2N5(2+)*2C24H20B(1-)

Conditions	Yield
In dichloromethane at 45℃; for 24h; Schlenk technique; Inert atmosphere;	100%

C19H17FeN5O2 + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C35H47B2FeN5O2

Conditions	Yield
In tetrahydrofuran for 16h;	100%

N-allyl-N,N-dimethyl-N-butylammonium chloride + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C17H35BN(1+)*Cl(1-)

Conditions	Yield
In tetrahydrofuran at 60℃; for 12h; Schlenk technique; Inert atmosphere;	100%
In tetrahydrofuran at 20℃; for 6h; Glovebox;	95%

N,N,N-triethylpent-4-en-1-aminium iodide + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C19H39BN(1+)*I(1-)

Conditions	Yield
In tetrahydrofuran at 60℃; for 12h; Schlenk technique; Inert atmosphere;	100%

N,N,N-triethylhex-5-en-1-aminium bromide + 9-bora-bicyclo[3.3.1]nonane (280-64-8) → C20H41BN(1+)*Br(1-)

Conditions	Yield
In tetrahydrofuran at 60℃; for 12h; Schlenk technique; Inert atmosphere;	100%

Upstream product

• 1552-12-1 1,5-cis,cis-cyclooctadiene 
• 22086-34-6 9-chloro-9-borabicyclo{3.3.1}nonane 
• 5259-72-3 cyclo-octa-1,5-diene 
• 21205-91-4 9-borabicyclo[3.3.1]nonane dimer 
• 14044-65-6 borane-THF 
• 149468-33-7 9-(di-tert-butylphosphanyl)-9-bora{3.3.1}bicyclononane 
• 70160-59-7 C₈H₁₄BBrS(CH₃)2 
• 70160-58-6 C₈H₁₄BClS(CH₃)2 
• 22560-16-3 lithium triethylborohydride 
• 16940-66-2 sodium tetrahydroborate 
• 19756-04-8 tetrakis(dimethylamido)zirconium (IV) 
• 187403-06-1 [C₈BH₁₄]2C₁₀H₆(NH)2 
• 13292-87-0 dimethylsulfide borane complex 
• 1378876-25-5 C₂₆H₄₇BNiO₂P₂ 

Downstream Products

• 23418-91-9 9-phenyl-9-borabicyclo[3.3.1]nonane 
• 23418-90-8 B-p-tolyl-9-borabicyclo[3.3.1]nonane 
• 65481-78-9 B-mesityl-9-borabicyclo[3.3.1]nonane 
• 64045-95-0 9-borabicyclo[3.3.1]nonane * pyridine 
• 93184-61-3 oct-3-yn-1-ylbenzene 
• 19780-12-2 5-dodecyne 
• 7206-28-2 (Z)-dodec-5-ene 
• 35354-39-3 cis-2-Methyl-7-octadecen 
• 56-35-9 bis(tri-n-butyltin)oxide 
• 93184-60-2 1-(3-Cyclohexenyl)-3-octyne 
• 54844-65-4 (Z)-6-heneicosen-11-one 
• 301310-36-1 (3E,5R,6R,7S)-7-azido-5,6,8-tribenzyloxy-3-tert-butylthio-1,3-octadiene 
• 180286-97-9 9-(3-phenylpropyl)-9-borabicyclo[3.3.1]nonane 
• 374754-93-5 (9-BBN)(CH₂)3(p-anisyl) 

Relevant academic research and scientific papers

A novel diaminoborate ligand system derived from 1,8-diaminonaphthalene and 9-BBN: Preparation of titanium and zirconium complexes and crystal structure of the titanium complex

1,8-Diaminonaphthalene reacts selectively with 1 equiv. of 9-BBN to form a bridging amine-aminoborane, and with 2 equiv. of 9-BBN to form a non-bridging bis(aminoborane); these aminoboranes give rise to a novel diaminoborate (4e,1-) ligand system by reactions with dimethylamides of titanium and zirconium.

Hydroboration Kinetics. 7. Kinetics and Mechanism of the Reduction of Aldehydes and Ketones with 9-Borabicyclononane Dimer

The kinetics of the reduction of a number of aldehydes and ketones with 9-borabicyclononane dimer, (9-BBN)2, was studied at 25.0 deg C.The reduction of aldehydes and reactive ketones followed first-order kinetic behavior; with less reactive ketones, intermediate or three-halves-order kinetics was observed.Thus the mechanism is very similar to that of the hydroboration of alkenes and alkynes by (9-BBN)2, involving 9-BBN monomer as the intermediate.The relative rates of reduction of representative aldehydes and ketones were determined by the competitive method since the kinetic study could not reveal the effect of the structure upon the reactivity.A comparison with NaBH4 shows that (9-BBN)2 is less susceptible to steric effects, though the same trend is observed with both reagents.Increasing the steric hindrance on one side of the carbonyl function in ketones leads to a modest rate decrease while that on both sides leads to a considerable rate decrease.Electron-withdrawing substituents decrease and electron-releasing ones increase the rate of reduction of aldehydes and ketones.These facts strongly suggest that the boron atom of the reducing species, 9-BBN monomer, is coordinated with the carbonyl oxygen during the reduction process.

Interactions of C?F Bonds with Hydridoboranes: Reduction, Borylation and Friedel–Crafts Alkylation

The stoichiometric reactions of the alkylfluorides 1-fluoroadamantane (Ad-F), fluorocyclohexane (Cy-F), 1-fluoropentane (Pent-F) and benzyl fluorides with secondary boranes pinacolborane (HBpin), catecholborane (HBcat), 9-borabicyclo(3.3.1)nonane (9-BBN)

Pincer-ligated nickel hydridoborate complexes: The dormant species in catalytic reduction of carbon dioxide with boranes

Nickel pincer complexes of the type [2,6-(R2PO) 2C6H3]NiH (R = tBu, 1a; R = iPr, 1b; R = cPe, 1c) react with BH3·THF to produce borohydride complexes [2,6-(R2/su

SALTS OF 2-FLUORO-N-METHYL-4-[7-(QUINOLIN-6-YL-METHYL)-IMIDAZO[1,2-b][1,2,4]TRIAZIN-2-YL]BENZAMIDE AND PROCESSES RELATED TO PREPARING THE SAME

The present invention is directed to dihydrochloric acid and dibenzenesulfonic acid salts of the c-Met kinase inhibitor 2-fluoro-N-methyl-4-[7-(quinolin-6-ylmethyl)-imidazo[1,2-b][1,2,4]triazin-2-yl]benzamide, and pharmaceutical compositions thereof, useful in the treatment of cancer and other diseases related to the dysregulation of kinase pathways. The present invention further relates to processes and intermediates for preparing 2-fluoro-N-methyl-4-[7-(quinolin-6-ylmethyl)imidazo[1,2-b][1,2,4]triazin-2-yl]benzamide, and salts thereof.

N-(2,4,6-trimethylborazinyl)-substituted boron, aluminum and titanium compounds

The N-lithioborazine LiH2N3B3Me 3, 1, reacts with organoboron halides not only to the respective borazinyl organylboranes but also by Me/halogen exchange. (Me2N) 2B-H2N3B3Me3 was obtained from 1 and (Me2N)2BCl. A new ten-membered B 6N4 ring system, 5, results on treatment of Cl(Me 2N)B-B(NMe2)Cl with 1. The B-N-borazinyl borazines 6-8 can be prepared from 1 and B-monohalo borazines. The synthesis of 2,4,6-trimethylborazinyl-aluminum and -titanium compounds is achieved only with mononuclear monohalides of Al(III) and Ti(IV). The 2,4,6-trimethylborazinyl- bis(piperidino)alane 9 and the tris(2,6-diisopropylphenoxo)-2,4,6- trimethylborazinyltitanium 10 were characterized by X-ray structure analysis. The distortion of the borazine ring by B and N substitution is discussed. In case of the N-substituted borazines YH2N3B 3Me3 the B-N bonds of the YNB2 units are elongated, e. g. for Y = PBr2 or (RO)3Ti, while N lithiation leads to a shortening of these B-N bond. These changes of bond lengths are also reflected by changes in the B1-N2 and B3-N3 bond lengths which become shorter in the presence of electron-withdrawing groups, but longer in case of Li substitution. Also, the bond angles B1-N2-B2 and B2-N3-B3 are affected by an increase of up to 128°.

Molecular addition compounds. 14. Convenient preparations of representative dialkylborane reagents using the new, highly reactive N- ethyl-N-isopropylaniline-borane reagent (BACH-EI(TM))

Convenient procedures for the preparation of representative dialkylborane reagents, diisopinocampheylborane, [1S]-2-diisocaranylborane, 9-borabicyclo[3,3,1]nonane, dicyclohexylborane and disiamylborane, using the new, highly reactive N-ethyl-N-isopropylaniline-borane reagent (BACH-EI(TM)) in dioxane and tetrahydrofuran are described.

Molecular addition compounds. 13. N,N-diisopropyl-n-isobutylamine-borane: The first highly reactive trialkylamine-borane reagent for hydroborations

N,N-Diisopropyl-N-isobutylamine (1) forms a stable liquid borane adduct (4.7 M in BH3), when diborane is bubbled into the neat amine. The adduct thus formed is stable indefinitely at room temperature under an inert atmosphere. Hydroboration studies with this new, highly reactive amine-borane adduct, H3B:NPri2Bui (2) and representative olefins, such as 1-hexene, styrene, β-pinene, cyclopentene, norbornene, cyclohexene, 2-methyl-2-butene, α-pinene, and 2,3-dimethyl-2-butene, were carried out at room temperature (22 ± 3°C) in selected solvents, tetrahydrofuran, dioxane, tert-butyl methyl ether, n-pentane, and dichloromethane. The reactions are faster in dioxane and n-pentane, requiring ～2 h for the hydroboration of simple, unhindered olefins to the trialkylborane stage.

Contributions to the Chemistry of Boron, 215. - Synthesis and Reactions of Monomeric Tetraorganyl-phosphanylboranes

The reaction of diorganyl-chloroboranes with lithium diorganyl- or lithium bis(trimethylsilyl)phosphides leads to the monomeric phosphanylboranes tBu2BPtBu2 (1), tBu2BP(SiMe3)2 (2), 9-BBNPtBu2 (3), 9-BBNP(SiMe3)2 (4), and Cy2BPtBu2 (5).These species were studied by NMR-spectroscopic methods.For further characterization reactions of the compounds 1, 3, and 5 have been investigated.Heating of 1 and 5 results in the formation of the dimeric phosphanylboranes tBu(H)BPtBu2 (8) and Cy(H)BPtBu2 (9) by dehydroboration.Dimers 8 and 9 are present as cis- and trans-isomers asconfirmed by X-ray structure analyses.The trans isomer of 9 shows a planar (BP)2 four-membered ring, whereas the ring of the cis-isomer of 8 is slightly folded.Furthermore, the reaction of 3 with 9H-9-BBN yields (μ-H)(μ-tBu2P)2 (14), whose bridged structure is proven by a crystal structure analysis.Oxidation of the phosphorus atom in 3 with sulfur leads to the S-boryl thiophosphinate tBu2(S)PS-9-BBN (16). Key Words: Phosphanylboranes, tetraorganyl/1,3,2,4-Diphosphadiboracyclobutane/Diboranes, μ-phosphanyl-/Thiophosphinate, S-boryl.