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Chemical Synthesis

Takasago Ligands

Introduction

Advantages

Representative Applications

Product Information


Introduction
The quest to find chiral catalysts capable of achieving high enantiomeric excess for a variety of asymmetric transformations has been an ongoing endeavor for the past 40 years. One of the most relevant reactions used to evaluate the different chiral ligands and complexes is the asymmetric hydrogenation. This technology has been one of the most studied and utilized in industry and has been rewarded the Nobel Prize in 2001 for the outstanding work accomplished by Professor Ryoji Noyori and William S. Knowles.

Introduction Structure Image

Reference:
Noyori, R.; Ohkuma, T. Angew. Chem.; Int. Ed. 2001, 40, 40.


The research team at Takasago International Corporation developed a series of ligands and complexes for a plethora of catalyzed asymmetric reactions. Based on a biphenyl architecture, several phosphine ligands have been synthesized. Two large families of ligands can be distinguished, BINAP and SEGPHOS®. BINAP is based on a bis naphthalene backbone with different phosphine derivatives. SEGPHOS® is based on a bis(1,3-benzodioxole) with different phosphine substituents. BINAP and SEGPHOS® are highly reactive and selective in a variety of asymmetric hydrogenation. In conjunction with ruthenium, rhodium, palladium and copper complexes, these ligands allow for enantioselectivities of up to >99%.

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Advantages

  • Atom-economical catalytic method
  • High yields and selectivities for a variety of reactions
  • Access to a variety of chiral building clocks in excellent yields

Representative Applications

Rhodium-Catalyzed 1,4-Addition of Arylboronic Acids to Coumarins

Chen et al. presented the asymmetric synthesis of arylated coumarins. The importance of this transformation with coumarin precursors is illustrated with the synthesis of (R)-tolterodine, a urological drug that can be readily obtain follwing the asymmetric arylation. Using SEGPHOS® and Rh(acac)(C2H4)2, the researchers were able to obtain the desired arylated coumarins with a yield of 88% and ee of 99.6%.

Rhodium-Catalyzed 1,4-Addition of Arylboronic Acids to Coumarins Image

Reference:
Lipshutz, B. H. et al. Org. Lett. 2006, 8, 2969.

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Asymmetric Hydrogenation of Amino Ketones

Ohkuma et al. reported a practical asymmetric hydrogenation reactions using mild hydrogen pressure with a wide scope. The access to chiral alcohol from amino ketone is important for the synthesis of physiologically active compounds. In this new process, a diphosphine/diamine Ru catalyst is utilized. This complex is based on DM-BINAP and 1,1-di-4-anysil-2-isopropyl-1,2-ethylenediamine (DAIPEN) and a ruthenium complex. Using a loading as low as 0.01 mol% of catalyst, the hydrogenation of various amino ketones was conducted with up to 99% yield and up to 99.8% ee. To illustrate the relevance of this new catalyst, Okuma et al. synthesized a series of known molecules used in drugs.

Asymmetric Hydrogenation of Amino Ketones Image

Reference:
Ohkuma, T. et al. J. Am. Chem. Soc. 2000, 122, 6510.



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Product Information

Product # Product Name Structure Add to Cart
693057 (S)-BINAP (S)-BINAP Structure
693030 (S)-T-BINAP (S)-T-BINAP Structure
693022 (S)-DM-BINAP (S)-DM-BINAP Structure
693014 (S)-H8-BINAP (S)-H8-BINAP Structure
693065 (R)-BINAP (R)-BINAP Structure
693049 (R)-T-BINAP (R)-T-BINAP Structure
692379 (R)-DM-BINAP (R)-DM-BINAP Structure
692387 (R)-H8-BINAP (R)-H8-BINAP Structure
693006 (S)-SEGPHOS® (S)-SEGPHOS Structure
692999 (S)-DM-SEGPHOS® (S)-DM-SEGPHOS Structure
692980 (S)-DTBM-SEGPHOS® (S)-DTBM-SEGPHOS Structure
692395 (R)-SEGPHOS® (R)-SEGPHOS Structure
692476 (R)-DM-SEGPHOS® (R)-DM-SEGPHOS Structure
692484 (R)-DTBM-SEGPHOS® (R)-DTBM-SEGPHOS Structure
693383 cBRIDP cBRIDP
693537 (R)-MOP
702943 Cy-vBRIDP Cy-vBRIDP
702951 Cy-cBRIDP Cy-cBRIDP
703907 RuCl(p-cymene)[(R,R)-Ts-DPEN] RuCl(p-cymene)[(R,R)-Ts-DPEN]</
703915 RuCl(p-cymene)[(S,S)-Ts-DPEN]
708682 RuCl[(R,R)-TsDPEN](mesitylene) RuCl[R,R)-TsDPEN](mesitylene)
708690 RuCl[(S,S)-FsDPEN](p-cymene) RuCl[(S,S)-FsDPEN](p-cymene)
708674 RuCl[(S,S)-TsDPEN](mesitylene)
711179 vBRIDP
708704 RuCl[(R,R)-FsDPEN](p-cymene)
692972 (S)-RuCl[(p-cymene(BINAP)Cl (S)-RuCl[(p-cymene(BINAP)Cl Structure
692964 (S)-RuCl[(p-cymene(T-BINAP)Cl (S)-RuCl[(p-cymene(T-BINAP)Cl Structure
693103 (S)-RuCl[(p-cymene(DM-BINAP)Cl (S)-RuCl[(p-cymene(DM-BINAP)Cl Structure
693111 (S)-RuCl[(p-cymene(H8-BINAP)Cl (S)-RuCl[(p-cymene(H8-BINAP)Cl Structure
692956 (S)-RuCl[(p-cymene(SEGPHOS®)Cl (S)-RuCl[(p-cymene(SEGPHOS)Cl Structure
692948 (S)-RuCl[(p-cymene(DM-SEGPHOS®)Cl (S)-RuCl[(p-cymene(DM-SEGPHOS)Cl Structure
693073 (S)-RuCl[(p-cymene(DTBM-SEGPHOS®)Cl (S)-RuCl[(p-cymene(DTBM-SEGPHOS)Cl Structure
692492 (R)-RuCl[(p-cymene(BINAP)Cl (<i>R</i>)-RuCl[(p-cymene(BINAP)Cl Structure
692506 (R)-RuCl[(p-cymene(T-BINAP)Cl (<i>R</i>)-RuCl[(p-cymene(T-BINAP)Cl Structure
692409 (R)-RuCl[(p-cymene(DM-BINAP)Cl (<i>R</i>)-RuCl[(p-cymene(DM-BINAP)Cl Structure
692514 (R)-RuCl[(p-cymene(H8-BINAP)Cl (<i>R</i>)-RuCl[(p-cymene(H8-BINAP)Cl Structure
692522 (R)-RuCl[(p-cymene(SEGPHOS®)Cl (R)-RuCl[(p-cymene(SEGPHOS)Cl Structure
692417 (R)-RuCl[(p-cymene(DM-SEGPHOS®)Cl (R)-RuCl[(p-cymene(DM-SEGPHOS)Cl Structure
692425 (R)-RuCl[(p-cymene(DTBM-SEGPHOS®)Cl (R)-RuCl[(p-cymene(DTBM-SEGPHOS)Cl Structure
693138 (S)-[(RuCl(BINAP))2(µ-Cl)3][NH2Me2] (S)-[(RuCl(BINAP))2(µ-Cl)3][NH2Me2] Structure
693146 (S)-[(RuCl(T-BINAP))2(µ-Cl)3][NH2Me2] (S)-[(RuCl(T-BINAP))2(µ-Cl)3][NH2Me2] Structure
693154 (S)-[(RuCl(DM-BINAP))2(µ-Cl)3][NH2Me2] (S)-[(RuCl(DM-BINAP))2(µ-Cl)3][NH2Me2] Structure
693324 (S)-[(RuCl(H8-BINAP))2(µ-Cl)3][NH2Me2] (S)-[(RuCl(H8-BINAP))2(µ-Cl)3][NH2Me2] Structure
693162 (S)-[(RuCl(SEGPHOS®))2(µ-Cl)3][NH2Me2] (S)-[(RuCl(SEGPHOS))2(µ-Cl)3][NH2Me2] Structure
693170 (S)-[(RuCl(DM-SEGPHOS®))2(µ-Cl)3][NH2Me2] (S)-[(RuCl(DM-SEGPHOS))2(µ-Cl)3][NH2Me2] Structure
692433 (R)-[(RuCl(BINAP))2(µ-Cl)3][NH2Me2] (R)-[(RuCl(BINAP))2(µ-Cl)3][NH2Me2] Structure
692441 (R)-[(RuCl(T-BINAP))2(µ-Cl)3][NH2Me2] (R)-[(RuCl(T-BINAP))2(µ-Cl)3][NH2Me2] Structure
692468 (R)-[(RuCl(DM-BINAP))2(µ-Cl)3][NH2Me2] (R)-[(RuCl(DM-BINAP))2(µ-Cl)3][NH2Me2] Structure
692190 (R)-[(RuCl(H8-BINAP))2(µ-Cl)3][NH2Me2] (R)-[(RuCl(H8-BINAP))2(µ-Cl)3][NH2Me2] Structure
692204 (R)-[(RuCl(SEGPHOS®))2(µ-Cl)3][NH2Me2] (R)-[(RuCl(SEGPHOS))2(µ-Cl)3][NH2Me2] Structure
692212 (R)-[(RuCl(DM-SEGPHOS®))2(µ-Cl)3][NH2Me2] (R)-[(RuCl(DM-SEGPHOS))2(µ-Cl)3][NH2Me2] Structure
693189 (S)-Ru(OAc)2(BINAP) (S)-Ru(OAc)2(BINAP) Structure
693197 (S)-Ru(OAc)2(T-BINAP) (S)-Ru(OAc)2(T-BINAP) Structure
693286 (S)-Ru(OAc)2(DM-BINAP) (S)-Ru(OAc)2(DM-BINAP) Structure
693278 (S)-Ru(OAc)2(H8-BINAP) (S)-Ru(OAc)2(H8-BINAP) Structure
693243 (S)-Ru(OAc)2(SEGPHOS®) (S)-Ru(OAc)2(SEGPHOS) Structure
693235 (S)-Ru(OAc)2(DM-SEGPHOS®) (S)-Ru(OAc)2(DM-SEGPHOS) Structure
692220 (R)-Ru(OAc)2(BINAP) (S)-Ru(OAc)2(BINAP) Structure
692239 (R)-Ru(OAc)2(T-BINAP) (S)-Ru(OAc)2(T-BINAP) Structure
692158 (R)-Ru(OAc)2(DM-BINAP) (S)-Ru(OAc)2(DM-BINAP) Structure
692166 (R)-Ru(OAc)2(H8-BINAP) (S)-Ru(OAc)2(H8-BINAP) Structure
692174 (R)-Ru(OAc)2(SEGPHOS®) (S)-Ru(OAc)2(SEGPHOS) Structure
692182 (R)-Ru(OAc)2(DM-SEGPHOS®) (S)-Ru(OAc)2(DM-SEGPHOS) Structure
693227 RuCl2[(S)-(DM-BINAP)][(S)-DAIPEN] RuCl2[(S)-(DM-BINAP)][(S)-DAIPEN] Structure
693251 RuCl2[(S)-(DM-BINAP)][(S,S)-DPEN] RuCl2[(S)-(DM-BINAP)][(S,S)-DPEN] Structure
693219 RuCl2[(S)-(SEGPHOS®)][(S)-DAIPEN] RuCl2[(S)-(SEGPHOS)][(S)-DAIPEN] Structure
693200 RuCl2[(S)-(SEGPHOS®)][(S,S)-DPEN] RuCl2[(S)-(SEGPHOS)][(S,S)-DPEN] Structure
692255 RuCl2[(R)-DM-BINAP][(R)-DAIPEN] RuCl2[(R)-DM-BINAP][(R)-DAIPEN] Structure
692301 RuCl2[(R)-DM-BINAP][(R,R)-DPEN] RuCl2[(R)-DM-BINAP][(R)-DAIPEN] Structure
692328 RuCl2[(R)-DM-SEGPHOS®][(R)-DAIPEN] RuCl2[(R)-DM-BINAP][(R)-DAIPEN] Structure
692336 RuCl2[(R)-DM-SEGPHOS®][(R,(R))-DPEN] RuCl2[(R)-DM-BINAP][(R)-DAIPEN] Structure

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