The Development of Enantioselective Rhodium‐Catalysed Hydroboration of Olefins

Rhodium-catalysed enantioselective hydroboration of olefins is a valuable synthetic transformation, typically employing a chiral catalyst and an achiral borane source. The pertinent chemo-, regio- and enantioselectivity issues of this reaction are discussed. However, the main emphasis of this review is on the evolution of catalytic asymmetric hydroboration. This has primarily relied upon the development and application of chiral bidentate P,P and P,N ligands which have exhibited varying degrees of success in this transformation.

[1]  C. Claver,et al.  In quest of factors that control the enantioselective catalytic Markovnikov hydroboration/oxidation of vinylarenes. , 2004, Chemistry.

[2]  P. Guiry,et al.  Preparation and resolution of a modular class of axially chiral quinazoline-containing ligands and their application in asymmetric rhodium-catalyzed olefin hydroboration. , 2004, The Journal of organic chemistry.

[3]  C. Crudden,et al.  Regio- and enantiocontrol in the room-temperature hydroboration of vinyl arenes with pinacol borane. , 2004, Journal of the American Chemical Society.

[4]  P. Guiry,et al.  The Development of Bidentate P,N Ligands for Asymmetric Catalysis , 2004 .

[5]  C. Claver,et al.  On the origin of regio- and stereoselectivity in the rhodium-catalyzed vinylarenes hydroboration reaction. , 2004, The Journal of organic chemistry.

[6]  C. Claver,et al.  New insights on the asymmetric hydroboration of perfluoroalkenes. , 2004, Chemical communications.

[7]  C. Crudden,et al.  Catalytic Asymmetric Hydroboration: Recent Advances and Applications in Carbon−Carbon Bond‐Forming Reactions , 2003 .

[8]  John M. Brown,et al.  Mechanistic and synthetic aspects of hydroboration with a simple atropisomeric ligand prepared from 1-(1′-(isoquinolyl)-2-naphthol , 2003 .

[9]  C. Claver,et al.  Efficiency of natural bentonite versus synthetic organo(bis-silantriolates) as supports towards the heterogenisation of asymmetric hydroboration , 2003 .

[10]  V. Gevorgyan,et al.  Catalytic enantioselective hydroboration of cyclopropenes. , 2003, Journal of the American Chemical Society.

[11]  A. J. Blacker,et al.  Practical Preparation and Resolution of 1-(2‘-Diphenylphosphino-1‘-naphthyl)isoquinoline: A Useful Ligand for Catalytic Asymmetric Synthesis , 2003 .

[12]  J. Cooper,et al.  Acyclic Stereoselective Boron Alkylation Reactions for the Asymmetric Synthesis of β-Substituted α-Amino Acid Derivatives , 2003 .

[13]  P. Knochel,et al.  New P, N-ferrocenyl ligands for rhodium-catalyzed hydroboration and palladium-catalyzed allylic alkylation , 2003 .

[14]  C. Claver,et al.  How to turn the catalytic asymmetric hydroboration reaction of vinylarenes into a recyclable process. , 2003, Chemistry.

[15]  L. Micouin,et al.  Reversal of enantioselectivity in the asymmetric rhodium- versus iridium-catalyzed hydroboration of meso substrates. , 2002, Journal of the American Chemical Society.

[16]  H. Schmalz,et al.  Identification of Suitable Ligands for a Transition Metal‐Catalyzed Reaction: Screening of a Modular Ligand Library in the Enantioselective Hydroboration of Styrene , 2002 .

[17]  A. Suzuki Cross-coupling reactions via organoboranes , 2002 .

[18]  S. Gougeon,et al.  Enantioselective desymmetrization of meso bicyclic hydrazines: a novel approach to the asymmetric synthesis of polysubstituted amino cyclopentanic cores. , 2002, The Journal of organic chemistry.

[19]  A. Chan,et al.  A new atropisomeric P,N ligand for rhodium-catalyzed asymmetric hydroboration. , 2002, The Journal of organic chemistry.

[20]  T. C. Morrill,et al.  Transition-metal-promoted hydroboration of alkenes: a unique reversal of regioselectivity. , 2002, The Journal of organic chemistry.

[21]  K. Maeda,et al.  Efficient kinetic resolution in hydroboration of 1,2-dihydronaphthalenes. , 2002, Chemical communications.

[22]  J. Hartwig,et al.  A new pathway for hydroamination. Mechanism of palladium-catalyzed addition of anilines to vinylarenes. , 2002, Journal of the American Chemical Society.

[23]  D. Trauner,et al.  The B-Alkyl Suzuki-Miyaura Cross-Coupling Reaction: Development, Mechanistic Study, and Applications in Natural Product Synthesis A list of abbreviations can be found at the end of the article. , 2001, Angewandte Chemie.

[24]  K. Chan,et al.  A Novel Synthesis of Atropisomeric P,N Ligands by Catalytic Phosphination Using Triarylphosphines , 2001 .

[25]  T. Imamoto,et al.  Asymmetric hydrogenation of enamides with Rh-BisP and Rh-miniPHOS catalysts. scope, limitations, and mechanism. , 2001, Journal of the American Chemical Society.

[26]  P. Knochel,et al.  NewC2-Symmetrical 1,2-Diphosphanes for the Efficient Rhodium-Catalyzed Asymmetric Hydroboration of Styrene Derivatives , 2001 .

[27]  C. Bianchini,et al.  Transition metal complexes with the C1-symmetric diphosphines (R)-(R)-3-benzyl-2,4-bis(diphenylphosphino)pentane and (R)-(R)-3-benzyl(p-sulphonate)-2,4-bis(diphenylphosphino)pentane sodium salt. Applications to enantioselective catalysis in different phase systems , 2001 .

[28]  G. Molander,et al.  Organolanthanide-catalyzed cyclization/boration of 1,5- and 1,6-Dienes. , 2001, Organic letters.

[29]  Takatoshi Ito,et al.  Cross-coupling reactions of potassium alkyltrifluoroborates with aryl and 1-alkenyl trifluoromethanesulfonates. , 2001, Organic letters.

[30]  P. Guiry,et al.  Axially Chiral Phosphinamine Ligands in Asymmetric Catalysis , 2000 .

[31]  Grützmacher,et al.  BABAR-Phos Rhodium Complexes: Reversible Metal Insertion into a Three-Membered Ring and Catalytic Hydroborations This work was supported by the ETH Zürich and the National Swiss Science Foundation. , 2000, Angewandte Chemie.

[32]  C. Bianchini,et al.  In Situ and Reactor Study of the Enantioselective Hydrogenation of Acetylacetone by Ruthenium Catalysis with the New Chiral Diphosphine Ligand (R)-(R)-3-Benzyl-2,4-bis(diphenylphosphino)pentane , 2000 .

[33]  Maeda,et al.  Catalytic asymmetric hydroboration/amination and alkylamination with rhodium complexes of 1,1'-(2-diarylphosphino-1-naphthyl)isoquinoline , 2000, Chemistry.

[34]  N. Miyaura,et al.  Rhodium- or Iridium-Catalyzed trans-Hydroboration of Terminal Alkynes, Giving (Z)-1-Alkenylboron Compounds , 2000 .

[35]  K. Chan,et al.  Synthesis of Biaryl P,N Ligands by Novel Palladium-Catalyzed Phosphination Using Triarylphosphines: Catalytic Application of C−P Activation , 2000 .

[36]  T. Ziegler,et al.  Comparative Density Functional Study of Associative and Dissociative Mechanisms in the Rhodium(I)-Catalyzed Olefin Hydroboration Reactions , 2000 .

[37]  Goddard,et al.  Preparation of alcohols from alkenes via the homologation of boronates with (Trimethylsilyl)diazomethane , 2000, Organic letters.

[38]  P. Guiry,et al.  Synthesis and resolution of 2-methyl-Quinazolinap, a new atropisomeric phosphinamine ligand for asymmetric catalysis , 2000 .

[39]  Sowa,et al.  Trifluoromethyl-substituted indenyl rhodium and iridium complexes are highly selective catalysts for directed hydroboration reactions , 2000, Organic letters.

[40]  P. Guiry,et al.  A new quinazoline-containing axially chiral ligand for asymmetric catalysis , 2000 .

[41]  C. Crudden,et al.  Catalytic Asymmetric Hydrocarboxylation and Hydrohydroxymethylation. A Two-Step Approach to the Enantioselective Functionalization of Vinylarenes , 1999 .

[42]  P. Ramachandran,et al.  Critical Role of Catalysts and Boranes for Controlling the Regioselectivity in the Rhodium-Catalyzed Hydroboration of Fluoroolefins , 1999 .

[43]  J. L. Ruiz,et al.  A chiral diphosphine containing hemilabile ether donor groups and its use in rhodium asymmetric hydroboration of styrene , 1999 .

[44]  P. Guiry,et al.  The preparation and resolution of 2-phenyl-Quinazolinap, a new atropisomeric phosphinamine ligand for asymmetric catalysis , 1999 .

[45]  R. Goddard,et al.  A new class of chiral diphosphines having planar chirality , 1999 .

[46]  J. Brunel,et al.  Enantioselective rhodium catalyzed hydroboration of olefins using chiral bis(aminophosphine) ligands , 1999 .

[47]  L. J. Wright,et al.  Synthesis and Structures of cis- and trans-[Os(Bcat)(aryl)(CO)2 (PPh3 )2 ]: Compounds of Relevance to the Metal-Catalyzed Hydroboration Reaction and the Metal-Mediated Borylation of Arenes. , 1999, Angewandte Chemie.

[48]  John M. Brown,et al.  The Scope of Catalytic Asymmetric Hydroboration/Oxidation with Rhodium Complexes of 1,1′-(2-Diarylphosphino-1-naphthyl)isoquinolines , 1999 .

[49]  M. Ogasawara,et al.  Rhodium-catalyzed asymmetric 1,4-addition of 2-alkenyl-1,3,2-benzodioxaboroles to α,β-unsaturated ketones , 1998 .

[50]  C. Bolm,et al.  Transition Metals for Organic Synthesis , 1998 .

[51]  In Su Lee,et al.  Synthesis of Planar Chiral (1,2-Disubstituted arene)chromium Tricarbonyl Compounds and Their Application in Asymmetric Hydroboration , 1998 .

[52]  L. J. Wright,et al.  Insertion of Ethyne into the Ru−B Bond of a Coordinatively Unsaturated Ruthenium Boryl Complex. X-ray Crystal Structure of Ru(CHCH[BOC6H4O])Cl(CO)(PPh3)2 , 1997 .

[53]  John M. Brown,et al.  Synthesis of 1′-(2-(diarylphosphino)1-naphthyl)isoquinolines; variation of the aryl substituent , 1997 .

[54]  I. Beletskaya,et al.  Hydroborations catalysed by transition metal complexes , 1997 .

[55]  A. Schnyder,et al.  Electronic Effects in Asymmetric Catalysis. Synthesis and Structure of Model Rhodium Complexes Containing Ferrocenyl Ligands for Use in the Hydroboration Reaction , 1997 .

[56]  J. Cossy,et al.  A short access to (+)-ptilocaulin , 1996 .

[57]  M. Srebnik,et al.  A study of hydroboration of alkenes and alkynes with pinacolborane catalyzed by transition metals , 1996 .

[58]  Xiaoming He,et al.  True Metal-Catalyzed Hydroboration with Titanium , 1996 .

[59]  M. Srebnik,et al.  Transition Metal-Catalyzed Hydroboration of and CCl4 Addition to Alkenes , 1996 .

[60]  A. Schnyder,et al.  Synthesis and Structure of Pyrazole-Containing Ferrocenyl Ligands for Asymmetric Catalysis , 1995 .

[61]  G. Whitlock,et al.  Catalytic asymmetric hydroboration with heterotopic P-N ligands: Trends in enantioselectivity with increased steric demand , 1995 .

[62]  D. Hibbs,et al.  Synthesis and chemistry of a new P-N chelating ligand; (R) and (S)-6-(2′-diphenylphosphino-1′-naphthyl)phenanthridine , 1995 .

[63]  S. Westcott,et al.  Transition Metal Catalyzed Diboration of Vinylarenes , 1995 .

[64]  M. Srebnik,et al.  Hydroboration of Alkynes with Pinacolborane Catalyzed by HZrCp2Cl , 1995 .

[65]  A. Schnyder,et al.  Strong Electronic Effects on Enantioselectivity in Rhodium‐Catalyzed Hydroborations with Novel Pyrazole‐Containing Ferrocenyl Ligands , 1995 .

[66]  P. Schleyer,et al.  An Ab Initio Investigation of the RhI‐Catalyzed Hydroboration of CC Bonds: Evidence for Hydrogen Migration in the Key Step , 1995 .

[67]  K. Morokuma,et al.  An ab initio molecular orbital study of the mechanism of the rhodium(I)-catalyzed olefin hydroboration reaction , 1994 .

[68]  L. Sneddon,et al.  Transition Metal-Promoted Reactions of Boron Hydrides. 14. A New Synthetic Route to B-Substituted Mono-, Di-, and Trialkylborazines, B-Vinyl-B,B-dialkylborazines, and B-Alkylpolyborazylenes via Rhodium-Catalyzed Borazine/Olefin Hydroboration Reactions , 1994 .

[69]  H. Jendralla,et al.  Efficient synthesis of (R)- and (S)-(6,6′-difluorobiphenyl-2,2′-diyl) bis(diphenylphosphine); electron-poor biphenyl-type ligands for transition metal catalysts. , 1994 .

[70]  K. Burgess,et al.  The importance of phosphine-to-rhodium ratios in enantioselective hydroborations , 1994 .

[71]  A. Togni,et al.  A Novel Easily Accessible Chiral Ferrocenyldiphosphine for Highly Enantioselective Hydrogenation, Allylic Alkylation, and Hydroboration Reactions , 1994 .

[72]  P. Guiry,et al.  Mechanistic and synthetic studies in catalytic allylic alkylation with palladium complexes of 1-(2-diphenylphosphino-1-naphthyl)isoquinoline , 1994 .

[73]  G. Kabalka,et al.  Nickel Catalyzed Hydroboration with Catecholborane , 1994 .

[74]  John M. Brown,et al.  Vinylborane formation in rhodium-catalyzed hydroboration of vinylarenes. Mechanism versus borane structure and relationship to silation , 1994 .

[75]  D. Seebach,et al.  Catalytic Enantioselective Hydrosilylation of Aromatic Ketones Using Rhodium Complexes of TADDOL-Derived Cyclic Phosphonites and Phosphites , 1993 .

[76]  Richard L. Harlow,et al.  Preparation and use of C2-symmetric bis(phospholanes): production of .alpha.-amino acid derivatives via highly enantioselective hydrogenation reactions , 1993 .

[77]  K. Burgess,et al.  Hydroboration reactions mediated by bis(mesityl)niobium: Beware of the trojan horse , 1993 .

[78]  K. Burgess,et al.  Ruthenium-catalyzed hydroborations of alkenes , 1993 .

[79]  Davidr . Evans,et al.  Samarium(III)-catalyzed hydroboration of olefins with catecholborane. A general approach to the synthesis of boronate esters , 1993 .

[80]  N. Miyaura,et al.  Convenient one-pot synthesis of vinylic sulfides from thioalkynes via a catalytic hydroboration-coupling sequence , 1993 .

[81]  S. Westcott,et al.  Nucleophile promoted degradation of catecholborane: consequences for transition metal-catalyzed hydroborations , 1993 .

[82]  S. Westcott,et al.  Insertion of alkenes into rhodium-boron bonds , 1993 .

[83]  John M. Brown,et al.  Synthesis and resolution of 1-(2-diphenylphosphino-1-naphthyl)isoquinoline; a PN chelating ligand for asymmetric catalysis. , 1993 .

[84]  N. Miyaura,et al.  Regio- and stereospecific preparation of .beta.-(alkylthio)alkenyl-1,3,2-benzodioxaboroles by nickel-catalyzed hydroboration of thioacetylenes with catecholborane , 1993 .

[85]  T. Marks,et al.  Organolanthanide-catalyzed hydroboration of olefins , 1992 .

[86]  K. Burgess,et al.  Reactions of catecholborane with Wilkinson's catalyst: implications for transition metal-catalyzed hydroborations of alkenes , 1992 .

[87]  K. Burgess,et al.  Stereochemically matched (and mismatched) bisphosphine ligands: DIOP-DIPAMP hybrids , 1992 .

[88]  Davidr . Evans,et al.  Mechanistic Study of the Rhodium(I)-Catalyzed Hydroboration Reaction , 1992 .

[89]  Davidr . Evans,et al.  Rhodium(I)- and iridium(I)-catalyzed hydroboration reactions: scope and synthetic applications , 1992 .

[90]  Tamio Hayashi,et al.  Palladium(0)-catalyzed hydroboration of 1-buten-3-ynes: preparation of allenylboranes , 1992 .

[91]  P. Knochel,et al.  Mild and stereoselective hydroborations of functionalized alkynes and alkenes using pinacolborane , 1992 .

[92]  H. Kurosawa,et al.  Recent developments in the chemistry of olefin complexes of palladium and platinum: Some novel findings as well as elaborate extensions , 1992 .

[93]  K. Burgess,et al.  On deuterium-labeling studies for probing rhodium-catalyzed hydroboration reactions [Erratum to document cited in CA114(21):206508c] , 1991 .

[94]  K. Burgess,et al.  Transition-metal promoted hydroborations of alkenes, emerging methodology for organic transformations , 1991 .

[95]  John M. Brown,et al.  CATALYTIC ASYMMETRIC HYDROBORATION WITH OXAZABOROLIDINES , 1991 .

[96]  K. Burgess,et al.  On deuterium-labeling studies for probing rhodium-catalyzed hydroboration reactions , 1991 .

[97]  L. Dai,et al.  Reversed regiochemistry in the hydroboration of vinylarenes catalyzed by neutral rhodium complexes and the related asymmetric version , 1991 .

[98]  Joseph S Merola,et al.  Synthesis and structure of a [(1,2-phenylenedioxy)boryl]iridium hydride complex: a model system for studying catalytic hydroboration , 1990 .

[99]  Davidr . Evans,et al.  The rhodium-catalyzed hydroboration of olefins: a mechanistic investigation , 1990 .

[100]  Tamio Hayashi,et al.  Catalytic asymmetric hydroboration of styrenes , 1989 .

[101]  K. Burgess,et al.  Enantioselective hydroboration mediated by homochiral rhodium catalysts , 1988 .

[102]  L. Sneddon,et al.  Transition-metal-promoted reactions of boron hydrides. 10. Rhodium-catalyzed syntheses of B-alkenylborazines , 1987 .

[103]  R. Crabtree,et al.  Directing effects in homogeneous hydrogenation with [Ir(cod)(PCy3)(py)]PF6 , 1986 .

[104]  R. Noyori,et al.  Practical synthesis of (R)- or (S)-2,2'-bis(diarylphosphino)-1,1'-binaphthyls (BINAPs) , 1986 .

[105]  H. Nöth,et al.  Catalytic Hydroboration with Rhodium Complexes , 1985 .

[106]  Y. Hamada,et al.  Asymmetric Synthesis Catalyzed by Chiral Ferrocenylphosphine–Transition Metal Complexes. I. Preparation of Chiral Ferrocenylphosphines , 1980 .

[107]  M. D. Fryzuk,et al.  Asymmetric synthesis. Production of optically active amino acids by catalytic hydrogenation. , 1977, Journal of the American Chemical Society.

[108]  B. D. Vineyard,et al.  Asymmetric hydrogenation. Rhodium chiral bisphosphine catalyst , 1977 .

[109]  Kazushi Ito,et al.  Oxidative addition of 4,4,6-trimethyl-1,3,2-dioxaborinane and benzo(1,3,2)dioxaborole to tris(triphenylphosphine)halogenorhodium. , 1975 .

[110]  H. Kagan,et al.  Asymmetric catalytic reduction with transition metal complexes. I. Catalytic system of rhodium(I) with (-)-2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane, a new chiral diphosphine , 1972 .

[111]  H. Brown,et al.  A New Powerful Reducing Agent—Sodium Borohydride in the Presence of Aluminum Chloride and Other Polyvalent Metal Halides1,2 , 1956 .

[112]  P. Evans,et al.  Modern rhodium-catalyzed organic reactions , 2005 .

[113]  C. Claver,et al.  An unprecedented recyclable catalyst system for asymmetric hydroboration. , 2001, Chemical communications.

[114]  C. Crudden,et al.  Homologations of boronate esters: the first observation of sequential insertions , 2000 .

[115]  P. Guiry,et al.  Enantioselective hydroboration of olefins catalysed bycationic rhodium complexes of2-phenylquinazolin-4-yl-2-(diphenylphosphino)naphthalene , 2000 .

[116]  Paul G. Hayes,et al.  Metal catalysed addition of B–H and N–H bonds to aminopropyl vinyl ethers , 2000 .

[117]  Jin Bum Kim,et al.  Asymmetric modular synthesis of cylindrically chiral FerroPHOS ligands for the Rh-catalyzed asymmetric hydroboration. , 2000, Chirality.

[118]  J. Maddaluno,et al.  Combining high pressure and catalysis: pinacol- or catecholborane hydroboration of functionalized olefins , 2000 .

[119]  Eric N. Jacobsen,et al.  Comprehensive asymmetric catalysis , 1999 .

[120]  C. Crudden,et al.  Catalytic asymmetric carbon–carbon bond forming reactions: preparation of optically enriched 2-aryl propionic acids by a catalytic asymmetric hydroboration–homologation sequence† , 1999 .

[121]  John M. Brown,et al.  Catalytic asymmetric hydroboration–amination , 1997 .

[122]  John M. Brown,et al.  Contrasting behaviour of related palladium complex-derived resolving agents. 8-H conformational locking of the 1-naphthyl side-chain , 1995 .

[123]  Y. Uozumi,et al.  Axially chiral allenylboranes: catalytic asymmetric synthesis by palladium-catalysed hydroboration of but-1-en-3-ynes and their reaction with an aldehyde , 1993 .

[124]  John M. Brown,et al.  Effective asymmetric hydroboration catalysed by a rhodium complex of 1-(2-diphenylphosphino-1-naphthyl)isoquinoline , 1993 .

[125]  K. Burgess,et al.  Enantioselective hydroborations catalyzed by rhodium(+1) complexes , 1991 .

[126]  N. Taylor,et al.  Reactions of catecholatoborane with phosphinorhodium complexes: molecular structures of [RhHCl(Bcat)(PPri3)2] and [{(Pri2PCH2)2}Rh{(η6-cat)Bcat}](cat = 1,2-O2C6H4) , 1991 .

[127]  Yutaka Nunokawa,et al.  LiBH4-promoted hydroboration of alkenes with 1,3,2-benzodioxaborole , 1991 .

[128]  Y. Matsumoto,et al.  Asymmetric hydroboration of styrenes catalyzed by cationic chiral phosphine-rhodium(I) complexes , 1991 .

[129]  N. Miyaura,et al.  Rhodium(i)-catalyzed asymmetric hydroboration of alkenes with 1,3,2-benzodioxaborole , 1990 .