- Axially Chiral Biaryl Monophosphine Oxides Enabled by Palladium/WJ-Phos-Catalyzed Asymmetric Suzuki-Miyaura Cross-coupling
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A highly enantioselective palladium/WJ-Phos-catalyzed Suzuki-Miyaura coupling reaction for efficient construction of axially chiral biaryl monophosphine oxides was developed. A series of axially chiral biaryl monophosphine oxides were obtained in good yields and with high enantioselectivities. The practicability of this reaction was validated in the straightforward synthesis of axially chiral biaryl monophosphine ligand and demonstrated by a 100-g-scale synthesis. Moreover, various functionalizations of the product make it as a platform molecule for synthesis of other chiral biaryl phosphines.
- Ji, Wangqin,Wu, Hai-Hong,Zhang, Junliang
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p. 1548 - 1554
(2020/02/04)
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- Asymmetric ketone hydroboration catalyzed by alkali metal complexes derived from BINOL ligands
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The ability of alkali metal complexes featuring functionalized BINOL-derived ligands to catalyze ketone hydroboration reactions was explored. The reduced products were formed in excellent yields and with variable enantioselectivities dependent upon the nature of the ligand and the alkali metal cation.
- Carden, Jamie L.,Melen, Rebecca L.,Newman, Paul D.,Ruddy, Adam J.,Willcox, Darren
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supporting information
p. 2417 - 2420
(2020/03/05)
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- Chiral Bifunctional Phosphine-Carboxylate Ligands for Palladium(0)-Catalyzed Enantioselective C?H Arylation
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Previous enantioselective Pd0-catalyzed C?H activation reactions proceeding via the concerted metalation-deprotonation mechanism employed either a chiral ancillary ligand, a chiral base, or a bimolecular mixture thereof. This study describes th
- Yang, Lei,Neuburger, Markus,Baudoin, Olivier
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supporting information
p. 1394 - 1398
(2018/01/05)
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- Palladium-catalyzed R2(O)P-directed C(sp2)-H activation
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In recent years, transition-metal-catalyzed inert C-H bond activation has developed rapidly and is a powerful protocol for the construction of new C-C or C-X bonds and the introduction of new functional groups. Our group has also developed a series of R2(O)P-directed Pd-catalyzed C-H functionalizations involving olefination, hydroxylation, acetoxylation, arylation, and acylation through an uncommon seven-membered cyclo-palladium pretransition state. Unlike previously used directing groups, the R2(O)P group acts as a directing group and is also involved in the construction of P,-hetero-ligands.
- Zhang, Hongyu,Yang, Shangdong
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p. 1280 - 1285
(2015/08/06)
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- Palladium-catalyzed R2(O)P directed C(sp2)-H acetoxylation
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A novel and efficient Pd-catalyzed C-H acetoxylation is described. The approach uses R2(O)P as a directing group to synthesize various substituted 2′-phosphorylbiphenyl-2-OAc compounds. Notably, the reaction exhibits smooth operation under mild conditions and shows good functional group tolerance. Products are obtained with high selectivity and yields. This journal is the Partner Organisations 2014.
- Zhang, Heng,Hu, Rong-Bin,Zhang, Xiao-Yu,Li, Shi-Xia,Yang, Shang-Dong
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supporting information
p. 4686 - 4689
(2014/05/06)
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- Pd(II)-catalyzed C(sp2)-H hydroxylation with R 2(O)P-coordinating group
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A novel R2(O)P-directed Pd(II)-catalyzed C-H hydroxylation to synthesize various substituted 2′-phosphorylbiphenyl-2-ol compounds is described. Notably, the reaction operates under mild conditions and shows good functional group tolerance, high selectivity, and yield.
- Zhang, Hong-Yu,Yi, Hong-Ming,Wang, Gang-Wei,Yang, Bin,Yang, Shang-Dong
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supporting information
p. 6186 - 6189
(2014/01/17)
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- Dendritic chiral phosphine lewis bases-catalyzed asymmetric aza-Morita-Baylis-Hillman reaction of N-sulfonated imines with activated olefins
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A series of polyether dendritic chiral phosphine Lewis bases was synthesized, and successfully applied to the asymmetric aza-Morita - Baylis - Hill -man reaction of N - sulfonated imines (N - arylmethyl -idene-4- methylbenzenesulfonamides) with methyl vin
- Liu, Ying-Hao,Shi, Min
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supporting information; body text
p. 122 - 128
(2009/04/10)
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- Chiral phosphine-catalyzed enantioselective construction of γ-butenolides through substitution of morita-baylis-hillman acetates with 2-trimethylsilyloxy furan
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Chiral multifunctional phosphine (R)-N-(2′-diphenylphosphanyl-[1,1-]binaphthalenyl-2-yl)methanesulfonamide L2 or (R)-N-(2′-diphenylphosphanyl-[1,1-]binaphthalenyl-2-yl)acetamide L3 is an efficient catalyst in the allylic substitutions of MBH acetates 1 with 2-trimethylsilyloxy furan 2 to provide γ-butenolides 3 in good to excellent yields and enantiomeric excesses in the presence of water. Copyright
- Jiang, Ying-Qing,Shi, Yong-Ling,Shi, Min
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p. 7202 - 7203
(2008/12/21)
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- Enantioselective conjugate addition of diethylzinc to acyclic enones using a copper phosphino-phenol complex as catalyst
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Newly designed phosphino-phenol 1c was found to be an efficient chiral auxiliary for copper-mediated asymmetric conjugate addition of diethylzinc to acyclic enones. High enantioselectivity up to >99% ee was achieved in the reaction of acyclic α,β-enones.
- Ito, Katsuji,Eno, Shuuichiro,Saito, Bunnai,Katsuki, Tsutomu
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p. 3981 - 3985
(2007/10/03)
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- A concise synthesis of 2-diarylphosphino-2′-methoxy-1,1′- binaphthalenes (MOPs) by simple resolution
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A practical synthesis of 2-diarylphosphino-2′-methoxy-1,1′- binaphthalene (MOPs) was provided by employing the etherification of 1,1′-bi-2,2′-naphthol on zeolite; the ring opening of the ether with lithium; the reaction with chlorodiaryl phosphine and the
- Luo, Yunfei,Wang, Feng,Zhu, Gangguo,Zhang, Zhaoguo
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- Axially chiral P,S-heterodonor ligands with a binaphthalene framework for palladium-catalyzed asymmetric allylic substitutions: Experimental investigation on the reversal of enantioselectivity between different alkyl groups on sulfur atom
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Axially chiral P,S-heterodonor ligands are effective promoters in the palladium-catalyzed asymmetric allylic substitution of 1,3-diphenylpropenyl acetate with dimethyl malonate to give the product in good yields with moderate to high ees and different abs
- Zhang, Wen,Shi, Min
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p. 3467 - 3476
(2007/10/03)
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- Palladium-catalyzed asymmetric allylic substitutions by axially chiral P,S-, S,S-, and S,O-heterodonor ligands with a binaphthalene framework
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Axially chiral P,S-heterodonor ligand L1 is quite effective in the asymmetric allylic substitution of 1,3-diphenylpropenyl acetate with dimethyl malonate. Its bidentate coordination pattern to Pd metal center with both P and S atoms has been unambiguously established by X-ray diffraction and NMR spectroscopic analyses. Axially chiral P,S-heterodonor ligand L1 is effective in the asymmetric allylic substitution of 1,3-diphenylpropenyl acetate with dimethyl malonate. Its bidentate coordination pattern to a Pd metal center with both P and S atoms has been unambiguously established by X-ray diffraction and NMR spectroscopic analyses. Herein, we further disclose that axially chiral S,S-heterodonor ligands L2-L4 are also effective in the same reaction to give the allylic alkylation product in moderate to good ee. However, the corresponding S,O-heterodonor ligands are not as effective as the corresponding P,S- or S,S-heterodonor ligands in the same asymmetric reaction.
- Zhang, Wen,Xu, Qin,Shi, Min
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p. 3161 - 3169
(2007/10/03)
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- Heterodimerization of Olefins. 1. Hydrovinylation Reactions of Olefins That Are Amenable to Asymmetric Catalysis
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Through a systematic examination of ligand and counterion effects, new protocols for a nearly quantitative and highly selective codimerization of ethylene and various functionalized vinylarenes have been discovered. In a typical reaction, 4-bromostyrene and ethylene undergo codimerization in the presence of 0.0035 equiv each of [(allyl)NiBr]2, triphenylphosphine, and AgOTf in CH2Cl2 at -56 °C to give 3-(4-bromophenyl) -1-butene in >98% yield and selectivity. Corresponding reactions with [(allyl)PdX]2 are much less efficient and less selective and may require further optimization before a viable system can be identified. Another useful protocol that gives comparable yield and selectivity involves the use of a single-component catalyst prepared from allyl 2-diphenylphosphinobenzoate, Ni(COD)2, and (C6F5)3B. Recognition of a synergistic relationship between a chiral hemilabile ligand (for example, (R)-2-methoxy-2′-diphenylphosphino-1,1′-binaphthyl, MOP) and a highly dissociated counteranion (BARF or SbF6) in an enantioselective version of the Ni-catalyzed reaction raises the prospects of developing a practical route for the synthesis of 3-arylbutenes. Several pharmaceutically relevant compounds, including widely used 2-arylpropionic acids, can be synthesized from these key intermediates. This reaction appears to be quite general. Synthesis of several new 2-diphenylphosphino-1,1-binaphthyl derivatives, prepared to probe the effect of hemilabile coordination on the efficiency and selectivity of the reaction, are also described.
- RajanBabu,Nomura, Nobuyoshi,Jin, Jian,Nandi, Malay,Park, Haengsoon,Sun, Xiufeng
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p. 8431 - 8446
(2007/10/03)
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- Optically active phosphine derivative having at least two vinyl groups, polymer produced using the same as monomer, and transition metal complexes of these
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A 2′-diarylphosphino-1,1′-biphenylen-2-yloxy(6,6′-divinyl-1,1′-binaphthalene-2,2′-diyloxy)phosphine derivative is disclosed, which is represented by general formula (I): wherein Ar is an optionally substituted phenyl or naphthyl; R1and R2
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- Optically active phosphine derivative having vinyl group, polymer produced using the same as monomer, and transition metal complexes of these
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A 6-vinyl-2'-diarylphosphino-1,1'-binaphthalen-2-yloxy(biphenylene-2,2'-diyloxy)phosphine derivative is disclosed, which is represented by general formula (I): wherein Ar is an optionally substituted phenyl or naphthyl; R1 and R2 each independently is a h
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- Phosphine derivative and polymer thereof and transition metal complex comprising the same
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Disclosed are a phosphine derivative represented by formula (I): wherein Ar represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, a transition metal complex comprising the phosphine derivative or a polyme
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- P/O ligand systems: Facile synthesis, structure, and catalytic tests of 2′-phosphanyl-1,1′-bipheny 1-2-ols and 2′-phosphanyl-1,1′-binaphthyl-2-ols
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A facile synthesis of 2′-phosphanyl-1,1′-biphenyl- and 2′-phosphanyl-l,1′-binaphthyl-2-ols and their silyl ethers has been developed, consisting of electron-transfer-catalyzed ring-opening of dibenzofuran and dinaphthofuran, respectively, subsequent reaction with chlorophosphanes, and work-up with acetic acid or ClSiMe3. Studies of the molecular and crystal structures reveal the presence of P...H-O bridging bonds in the more basic /BuPhP derivative and a nearly perpendicular arrangement of the aryl planes in the biphenyl derivatives. The barrier to rotation of the aryl planes about the C-C axis was determined by NMR in the case of the P-asymmetric derivative 3d, using the appearance of diastereoisomers by atropisomerism and P-asymmetry. Comparative screening tests of the title compounds, phosphanylphenols and phosphanylnaphthols in homogeneous Rh-catalyzed reactions demonstrate catalytic activity in hydroformylation reactions and superior properties of the biphenyl- and binaphthyl-2-ol derivatives in relation to other P-O ligands. WILEY-VCH Verlag GmbH, 1997.
- Kadyrov, Renat,Heinicke, Joachim,Kindermann, Markus K.,Heller, Detlef,Fischer, Christine,Selke, Ruediger,Fischer, Axel K.,Jones, Peter G.
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p. 1663 - 1670
(2007/10/03)
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- Novel Heterobidentate Ligands for Asymmetric Catalysis: Synthesis and Rhodium-catalysed Reactions of S-Alkyl (R)-2-Diphenylphosphino-1,1'-binaphthyl-2'-thiol
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Atropisomerically pure S-alkyl (R)-2-diphenylphosphino-1,1'-binaphthyl-2'-thiol derivatives have been synthesized through a multistep reaction sequence starting from (R)-binaphthol.Pd(II) and Rh(II) complexes containing the S-methyl derivative 14 as a chelate ligand have been prepared and characterized.Rh(I) complexes containing 14 or the S-iso-propyl derivative 15 effectively catalyse the asymmetric hydroformylation of styrene and the hydrogen transfer reduction of acetophenone.
- Gladiali, Serafino,Dore, Antonio,Fabbri, Davide
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p. 1143 - 1146
(2007/10/02)
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- Stereospecific functionalization of (R)-(-)-1,1'-BI-2-naphthol triflate
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Several examples of transition metal mediated functionalization of chiral 1,1'-bi-2-naphthol triflate are described which proceed with complete retention of substrate chirality. The transformation described demonstrate the potential of Pd(0) mediated reactions for the stereoselective transformation of the C-O bonds in this substrate.
- Kurz,Lee,Morgans Jr.,Waldyke,Ward
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p. 6321 - 6324
(2007/10/02)
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