Borane Dimethyl Sulfide

[13292-87-0] C2H9BS (MW 75.96) InChI = 1S/C2H6S.BH3/c1-3-2;/h1-2H3;1H3 InChIKey = RMHDLBZYPISZOI-UHFFFAOYSA-N (hydroborating and reducing agent) Alternate Name: BMS. Physical Data: d420 = 0.801 g cm−3. Solubility: sol dichloromethane, benzene, toluene, xylene, hexane, diethyl ether, diglyme, DME, and ethyl acetate; insol but reacts slowly with water; reacts with alcohols, acetone. Form Supplied in: neat complex, colorless liquid, ca. 10 M in BH3; contains slight excess of dimethyl sulfide. Analysis of Reagent Purity: active hydride is determined by hydrolysis of an aliquot in glycerol–water–methanol mixture and measuring the hydrogen evolved according to a standard procedure.3a 11B NMR (CH2Cl2) δ −20.1 ppm (q, JB–H = 104 Hz).4 Preparative Method: Diborane generated by the reaction of Sodium Borohydride with Boron Trifluoride Etherate in diglyme3 is absorbed in Dimethyl Sulfide. Purification: commercial reagent can be purified and freed of excess dimethyl sulfide by vacuum transfer.2 Handling, Storage, and Precautions: use in a fume hood; flammable liquid with stench; reacts with atmospheric moisture forming a crust of boric acid. Store and handle under nitrogen or argon. Stable indefinitely when kept at 0 °C. Stable for prolonged periods at rt.

[1]  Gang Zhao,et al.  Polymer-supported chiral sulfonamide catalyzed one-pot reduction of β-keto nitriles: a practical synthesis of (R)-fluoxetine and (R)-duloxetine , 2005 .

[2]  B. Shaw,et al.  Synthesis of nucleoside boranophosphoramidate prodrugs conjugated with amino acids. , 2005, The Journal of organic chemistry.

[3]  Tomoaki Hasui,et al.  Synthesis and Reactions of Cyclic Silylboranes , 2005 .

[4]  Â. Fátima,et al.  Asymmetric reduction of prochiral ketones using in situ generated oxazaborolidine derived from (1S,2S,3R,4R)-3-amino-7,7-dimethoxynorbornan-2-ol. An efficient synthesis of enantiopure (R)-tomoxetine , 2005 .

[5]  V. Åberg,et al.  Microwave-assisted synthesis of highly substituted aminomethylated 2-pyridones. , 2004, The Journal of organic chemistry.

[6]  B. Shaw,et al.  Convenient synthesis of nucleoside borane diphosphate analogues: deoxy- and ribonucleoside 5'-P(alpha)-boranodiphosphates. , 2004, The Journal of organic chemistry.

[7]  Jiaxi Xu,et al.  Influences of electronic effects and anions on the enantioselectivity in the oxazaborolidine-catalyzed asymmetric borane reduction of ketones. , 2004, The Journal of organic chemistry.

[8]  R. Stick,et al.  The Synthesis of a D-Glucose-like Piperidin-2-one: Isofagomine Lactam , 2004 .

[9]  J. C. Thomas,et al.  Platinum-alkyl and hydride complexes supported by a tris(phosphino)borate ligand: structural and spectroscopic studies , 2004 .

[10]  I. Manners,et al.  Linear hybrid aminoborane/phosphinoborane chains: synthesis, proton-hydride interactions, and thermolysis behavior. , 2004, Inorganic chemistry.

[11]  D. Crich,et al.  Asymmetric synthesis of highly substituted beta-nitro alcohols and enantiomerically enriched 4,4,5-trisubstituted oxazolidinones. , 2003, The Journal of organic chemistry.

[12]  S. Humbel,et al.  Configurational stability of chlorophosphines. , 2003, Inorganic chemistry.

[13]  L. Toupet,et al.  B(C6F5)3-catalyzed formation of B-P bonds by dehydrocoupling of phosphine-boranes. , 2003, Chemical communications.

[14]  A. Tagarelli,et al.  Stereoselective Complete Reduction of a-Alkyl--ketonitriles toanti ?-Amino Alcohols , 2002 .

[15]  Joachim Bill,et al.  Si-B-C-N ceramic precursors derived from dichlorodivinylsilane and chlorotrivinylsilane. 1. Precursor synthesis , 2002 .

[16]  B. Shaw,et al.  Synthesis of prodrug candidates: conjugates of amino acid with nucleoside boranophosphate. , 2002, Organic letters.

[17]  A. M. Gómez,et al.  Unexpected remarkable stability of primary ozonides derived from alkenyl stannanes. One-pot synthesis of 1,2-diols from alkynes. , 2002, Organic letters.

[18]  S. Rinaldi,et al.  One-pot highly stereoselective reduction of β-keto amides to syn-γ-aminols , 2001 .

[19]  B. Shaw,et al.  Boranophosphates as mimics of natural phosphodiesters in DNA. , 2001, Current medicinal chemistry.

[20]  C. Bauduin,et al.  Chemo-, regio- and stereoselective conversion of P-chirogenic phosphorus borane complexes into their PO or PS derivatives , 2001 .

[21]  G. Zhao,et al.  Asymmetric borane reduction of prochiral ketones by polymer-supported chiral sulfonamides. , 2001, The Journal of organic chemistry.

[22]  M. Parvez,et al.  Synthesis and applications of (R)- and (S)-7,7′-dimethoxy-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene , 2000 .

[23]  H. Grondey,et al.  Synthesis, structure and polymerization behaviour of borane adducts of a phosphorus-bridged [1]ferrocenophane, [(η-C5H4)2FePPh] , 2000 .

[24]  A. Dobó,et al.  One-pot transformation of cyclic phosphine oxides to phosphine–boranes by dimethyl sulfide–borane , 2000 .

[25]  S. Gilbertson,et al.  Palladium-Catalyzed Synthesis of Vinyl Phosphines from Ketones. , 1999 .

[26]  Gang Zhao,et al.  Catalytic enantioselective borane reduction of aromatic ketones with sulfonyl (S)-prolinol , 1999 .

[27]  A. Riera,et al.  A NEW FAMILY OF MODULAR CHIRAL LIGANDS FOR THE CATALYTIC ENANTIOSELECTIVE REDUCTION OF PROCHIRAL KETONES , 1999 .

[28]  Y. Xiong,et al.  RESOLUTION OF RACEMIC 1,1'-BI-2-NAPHTHOL USING (S)-PROLINE VIA A CYCLIC BORATE ESTER , 1999 .

[29]  A. Chan,et al.  New 1,3-amino alcohols derived from ketopinic acid and their application in catalytic enantioselective reduction of prochiral ketones , 1999 .

[30]  J. Brunel,et al.  Phosphane–boranes: synthesis, characterization and synthetic applications , 1998 .

[31]  H. Brown,et al.  Hydroboration. 96. Synthesis and Chemistry of Sterically Modified α-Pinene-Related 2-Organylapoisopinocampheylchloro- and -bromoboranes, Potentially Valuable for Asymmetric Hydroboration , 1998 .

[32]  T. Livinghouse,et al.  A Direct Synthesis of P-Chiral Phosphine−Boranes via Dynamic Resolution of Lithiated Racemic tert-Butylphenylphosphine−Borane with (−)-Sparteine , 1998 .

[33]  A. Romero,et al.  Synthesis of the Selective D2 Receptor Agonist PNU-95666E from d-Phenylalanine Using a Sequential Oxidative Cyclization Strategy , 1997 .

[34]  A. Granados,et al.  Unexpected Formation of 1,3-Diols from Unsaturated Chromium Fischer Carbene Complexes and Borane , 1997 .

[35]  M. Yates.  One-pot conversion of olefins to carbonyl compounds by hydroboration / NMO-TPAP oxidation , 1997 .

[36]  G. Gray,et al.  Reductive cleavage of permethylated polysaccharides with borane-methyl sulfide complex and butyltin trichloride. , 1997, Carbohydrate research.

[37]  N. Alcock,et al.  PHOSPHINAMIDES CATALYSTS CONTAINING A STEREOGENIC PHOSPHORUS ATOM FOR THE ASYMMETRIC REDUCTION OF KETONES BY BORANE , 1997 .

[38]  Li Liu,et al.  The steric effect and enantioselectivity of chiral 2,2-disubstituted thiaprolinol derivatives as ligands for borane reduction of aromatic ketones and for diethylzinc addition to aromatic aldehydes , 1996 .

[39]  Junqi Li,et al.  The Endocyclic Restriction Test: Investigation of the Geometries of Nucleophilic Substitution at Phosphorus(III) and Phosphorus(V) , 1996 .

[40]  R. Rathore,et al.  EFFICIENT HYDROGENATION OF STERICALLY HINDERED OLEFINS WITH BORANE-METHYL SULFIDE COMPLEX , 1996 .

[41]  F. Fotiadu,et al.  Enantioselective reduction of ketones by borane catalysed by oxazaphospholidine oxides , 1996 .

[42]  I. Oh,et al.  Reductive cleavage of glycosides with borane complexes in the presence of boron trifluoride etherate. , 1995, Carbohydrate research.

[43]  Takao Inoue,et al.  Synthesis and Properties of New Five-Membered Heterocyclic Compounds Containing a P-B-S Linkage , 1995 .

[44]  Davidr . Evans,et al.  ENANTIOSELECTIVE DEPROTONATION AS A VEHICLE FOR THE ASYMMETRIC SYNTHESIS OF C2-SYMMETRIC P-CHIRAL DIPHOSPHINES , 1995 .

[45]  F. Montforts,et al.  Enantioselective synthesis of hematoporphyrin stereoisomers , 1995 .

[46]  C. Cazé,et al.  Chiral oxazaborolidines bound via the boron atom to polymers prepared using 2-vinylthiophene: polymer-supported catalysts for the enantioselective reduction of prochiral ketones by borane , 1995 .

[47]  M. Zabłocka,et al.  Preparation of Scalemic P-Chiral Phosphines and Their Derivatives , 1994 .

[48]  R. Hunter,et al.  A selectivity study of activated ketal reduction with borane dimethyl sulfide , 1993 .

[49]  M. Srebnik,et al.  Photochemistry of trivinylboranes: Preparation of anti-adducts of hydroboranes and alkynes☆ , 1993 .

[50]  H. Cantow,et al.  Novel staining method for transmission electron microscopic investigations of semicrystalline polyesters , 1993 .

[51]  A. W. Douglas,et al.  A practical process for the preparation of tetrahydro-1-methyl-3,3-diphenyl-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborole-borane. A highly enantioselective stoichiometric and catalytic reducing agent , 1993 .

[52]  M. Srebnik,et al.  ASYMMETRIC BORON-CATALYZED REACTIONS , 1993 .

[53]  H. Brown,et al.  Hydroboration. 89. Preparation of Diborane, a sterically hindered monoalkylborane. Comparison with thexylborane , 1993 .

[54]  A. Foucaud,et al.  Reaction of dichlorocarbene with 1,2-dihydro 1,2 λ3-azaphosphinine-boranes : dichlorocyclopropanation and insertion into boron-hydrogen bond , 1993 .

[55]  W. T. Wipke,et al.  Novel conversion of aldehydes to boronic esters. Simultaneous IGOR2 computer generation and experimental observation of an unusual rearrangement of α-aminoboranes , 1993 .

[56]  H. Brown,et al.  Organoboranes for synthesis. 14. Convenient procedures for the direct oxidation of organoboranes from terminal alkenes to carboxylic acids , 1992 .

[57]  P. Pellon.  Phosphine-boranes in synthesis. Borane as an efficient protecting group in the preparation of functionalized phosphines , 1992 .

[58]  Yutaka Nunokawa,et al.  Ready preparation of trialkoxyboranes and dialkoxyboranes by LiBEt3H-promoted reaction of BH3 in tetrahydrofuran with alcohols , 1992 .

[59]  Kazuya Koga,et al.  A revised mechanism for chemoselective reduction of esters with borane-dimethyl sulfide complex and catalytic sodium tetrahydroborate directed by adjacent hydroxyl group , 1992 .

[60]  I. Fleming,et al.  The regiochemistry and stereochemistry of the hydroboration of allylsilanes , 1992 .

[61]  N. Ramsden,et al.  Synthesis of, and lack of inhibition of a rhamnosidase by, both enantiomers of deoxyrhamnojirimycin and rhamnolactam: β-mannosidase inhibition by δ-lactams , 1992 .

[62]  M. L. Corre,et al.  Effect of the Temperature on the Stoichiometry of Borane Dimethyl Sulfide Reduction of Secondary and Tertiary Amides , 1991 .

[63]  S. Cron,et al.  Reaction of borane-dimethyl sulfide complex with aromatic acids: access to methyl compounds or to benzyl dimethyl sulphonium salts. , 1991 .

[64]  J. Michael,et al.  Reduction of activated ketals with borane-dimethyl sulphide , 1991 .

[65]  H. Brown,et al.  Hydroboration. LXXXVI, Convenient conversion of aldehydes and ketones into the corresponding alkenes via hydroboration of their enamines. A remarkably simple synthesis of either (Z)- or (E)-alkenes , 1991 .

[66]  D. Tschaen,et al.  A Practical, One-Pot Preparation of Diisopinocampheylchloroborane , 1991 .

[67]  I. Hall,et al.  From boron analogues of amino acids to boronated DNA: potential new pharmaceuticals and neutron capture agents , 1991 .

[68]  J. Kraus,et al.  Synthesis of New 2,5-Substituted 1,3-Oxathiolanes. Intermediates in Nucleoside Chemistry , 1991 .

[69]  C. Stevens,et al.  A convenient method for the synthesis of β-chloroamines by electrophilic reduction of α-chloroimines , 1991 .

[70]  J. K. Haken,et al.  Gas chromatography of homologous esters . XXXIV, Alkyl borate and boronate esters , 1991 .

[71]  S. Siddiqi,et al.  Synthesis of (1R,4R)- and (1S,4S)-2,5-diazabicyclo[2.2.1]heptanes and their N-substituted derivatives , 1990 .

[72]  B. P. Roberts,et al.  Homolytic reactions of ligated boranes. Part 15. Comparative studies of amine–boranes as donor polarity reversal catalysts for hydrogen-atom abstraction , 1990 .

[73]  Y. Hisaeda,et al.  Preparation and molecular recognition behavior of a hexapus azaparacyclophane , 1990 .

[74]  J. Soderquist,et al.  1-Silacyclohexan-4-ones and 1-germacyclohexan-4-ones: precursors to metalla-pharmaceuticals via boracycles , 1989 .

[75]  L. Flippin,et al.  A convenient method for the reduction of ozonides to alcohols with borane-dimethyl sulfide complex , 1989 .

[76]  D. Bierer,et al.  Trimethylsilyl esters: protection of carboxylic acids during hydroboration reactions , 1989 .

[77]  N. N. Joshi,et al.  Hydroboration of terpenes. 9. A simple improved procedure for upgrading the optical purity of commercially available .alpha.- and .beta.-pinenes. Conversion of (+)-.alpha.-pinene to (+)-.beta.-pinene via hydroboration-isomerization , 1988 .

[78]  H. Brown,et al.  Hydroboration. 83. Asymmetric hydroboration of representative cis disubstituted and heterocyclic olefins with dicaranylboranes of high enantiomeric purity , 1988 .

[79]  A. Dicko,et al.  New Preparation of Aminoboronic Acids , 1988 .

[80]  M. Venuti,et al.  Borane-Methyl Sulfide Reductive Cyclization of ω-Ester Alkylamides: A Convenient Synthesis of N-Substituted Cyclic Amines , 1988 .

[81]  Shwn-Ji H. Lee,et al.  The asymmetric hydroboration of simple alkenylsilanes: chiral α-silylalkyl- boranes and alcohols , 1988 .

[82]  R. Contreras,et al.  Boron-11 nuclear magnetic resonance study of the reactions of 2-functionalized pyridines with borane–tetrahydrofuran and –dimethyl sulphide. Formation of borinic estes and N → B bond energy differences in five- and six-membered ring borates , 1988 .

[83]  E. Corey,et al.  Highly enantioselective borane reduction of ketones catalyzed by chiral oxazaborolidines. Mechanism and synthetic implications , 1987 .

[84]  H. Brown,et al.  Hydroboration. 81. Synthesis of 2-(dialkylamino)boronic esters and acids via hydroboration of enamines. A convenient preparation of .beta.-dialkylamino alcohols , 1987 .

[85]  J. Soderquist,et al.  Synthesis through the interconversion of methoxyboranes and boron hydrides. 9-BBN systems , 1987 .

[86]  A. C. Richardson,et al.  Enantiospecific synthesis of (6R,7S,8aR)-dihydroxyindolizidine and (6R,7R,8S,8aR)-trihydroxyindolizidine from D-glucose , 1987 .

[87]  H. Brown,et al.  Hydroboration of Heterocycles Olefins — A Versatile Route for the Synthesis of Both Racemic and Optically Active Heterocyclic Compounds , 1987 .

[88]  H. Brown,et al.  Hydroboration. 77. Hydroboration of cyclic dienes with representative hydroborating agents , 1986 .

[89]  H. Brown,et al.  Hydroboration. 75. Directive effects in the hydroboration of vinyl and propenyl heterocycles with representative hydroborating agents , 1986 .

[90]  H. Brown,et al.  Organoboranes for synthesis. 4 : Oxidation of organoboranes with pyridinium chlorochromate. A direct synthesis of aldehydes from terminal alkenes via hydroboration , 1986 .

[91]  R. Haltiwanger,et al.  Synthesis and crystal structure of an optically active, internally coordinated alkylchloroborane. The boron-centered anomeric effect , 1985 .

[92]  H. Brown,et al.  Hydroboration. 71. Hydroboration of representative heterocyclic olefins with borane-methyl sulfide, 9-borabicyclo[3.3.1]nonane, dicyclohexylborane, and disiamylborane. Synthesis of heterocyclic alcohols , 1985 .

[93]  R. Naik,et al.  Hydroboration. 67. Cyclic hydroboration of acyclic .alpha.,.omega.-dienes with 9-borabicyclo[3.3.1]nonane/borane-dimethyl sulfide , 1984 .

[94]  H. Brown,et al.  Hydroboration. 68. Chiral synthesis via organoboranes. 1. A simple procedure to achieve products of essentially 100% optical purity in hydroboration of alkenes with monoisopinocampheylborane. Synthesis of boronic esters and derived products of very high enantiomeric purities , 1984 .

[95]  G. Pai,et al.  Organoboranes: XXVIII. Convenient procedures for the synthesis of borinane☆ , 1983 .

[96]  Davidr . Evans,et al.  Acyclic diastereoselection in the hydroboration process. Documented cases of 1,3-asymmetric induction , 1983 .

[97]  H. Brown,et al.  Selective reductions. 29. A simple technique to achieve an enhanced rate of reduction of representative organic compounds by borane-dimethyl sulfide , 1982 .

[98]  K. Nicolaou,et al.  Carbohydrates in organic synthesis. Synthesis of 16-membered-ring macrolide antibiotics. 5. Total synthesis of O-mycinosyltylonolide: synthesis of key intermediates , 1982 .

[99]  S. Krishnamurthy,et al.  A HIGHLY EFFICIENT AND GENERAL N-MONOMETHYLATION OF FUNCTIONALIZED PRIMARY AMINES VIA FORMYLATION AND BORANE-METHYL SULFIDE REDUCTION , 1982 .

[100]  Stephan B. Hadley,et al.  Reduction of α,α-Dihaloketones with Electrophilic and Nucleophilic Reducing Agents , 1982 .

[101]  G. L. Larson,et al.  The Reaction of Trimethylsilyl Esters with Metal Hydride Reducing Agents. Protection of Carboxylic Acids as Their Trimethylsilyl Ester During Hydroboration , 1982 .

[102]  R. O. Hutchins,et al.  UTILITY AND APPLICATIONS OF BORANE DIMETHYLSULFIDE IN ORGANIC SYNTHESIS. A REVIEW , 1981 .

[103]  Joseph A. Miller,et al.  A Convenient Synthesis of Acylsilanes via Hydroboration-Oxidation of Silylacetylenes , 1981 .

[104]  R. Rodrigo,et al.  Potential isobenzofurans: their use in the synthesis of naturally occurring 1-arylnaphthalide lignans , 1980 .

[105]  J. Stille,et al.  Asymmetric hydroformylation and hydrocarboxylation of enamides. Synthesis of alanine and proline , 1980 .

[106]  H. Brown,et al.  A remarkable inversion in the selective oxidation of organoboranes and thioethers , 1980 .

[107]  H. Brown,et al.  FACILE OXIDATION OF TRIALKYL BORATES TO ALDEHYDES AND KETONES WITH PYRIDINIUM CHLOROCHROMATE. A REMARKABLE OXIDIZABILITY OF SUCH BORATE ESTERS AS COMPARED TO ACETATES , 1979 .

[108]  H. Brown,et al.  A Convenient Conversion of Carboxylic Acids into Aldehydes , 1979 .

[109]  G. Schmid,et al.  Synthetic studies on polyether antibiotics. 5. Total synthesis of monensin. 2. Stereocontrolled synthesis of the right half of monensin , 1979 .

[110]  H. Brown,et al.  Hydroboration. 45. New, convenient preparations of representative borane reagents utilizing borane-methyl sulfide , 1977 .

[111]  C. F. Lane,et al.  Organic synthesis using borane-methyl sulfide. II. Reduction of aromatic carboxylic acids in the presence of trimethyl borate , 1974 .

[112]  C. F. Lane.  Organic synthesis using borane-methyl sulfide. Hydroboration-oxidation of alkenes , 1974 .

[113]  R. Adams,et al.  Dimethyl sulfide-borane. Convenient hydroborating agent , 1971 .

[114]  R. Adams,et al.  (S-B) 3-(Methylthio)propylborane, a distillable monoalkylborane , 1971 .

[115]  Z. Polívka,et al.  Hydroboration of unsaturated amines. IV. Hydroboration of ω-dimethylaminoalkenes , 1970 .

[116]  S. Shore,et al.  Boron Heterocycles. III. The Effect of Borane Lewis Acid on Apparent Base Strength. New Examples of Base Strength Reversal1,2 , 1966 .

[117]  Franz v. Hemmelmayr.  Über das Ononin , 1901 .