- A Diastereodivergent and Enantioselective Approach to syn- And anti-Diamines: Development of 2-Azatrienes for Cu-Catalyzed Reductive Couplings with Imines That Furnish Allylic Amines
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We introduce a new reagent class, 2-azatrienes, as a platform for catalytic enantioselective synthesis of allylic amines. Herein, we demonstrate their promise by a diastereodivergent synthesis of syn- and anti-1,2-diamines through their Cu-bis(phosphine)-catalyzed reductive couplings with imines. With Ph-BPE as the supporting ligand, anti-diamines are obtained (up to 91% yield, >20:1 dr, and >99:1 er), and with the rarely utilized t-Bu-BDPP, syn-diamines are generated (up to 76% yield, 1:>20 dr, and 97:3 er).
- Zhou, Pengfei,Shao, Xinxin,Malcolmson, Steven J.
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- (Dicyclohexylphosphino)borane, BH3PH(C6H11)2, a precursor to water-soluble phosphine ligands
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(Dicyclohexylphosphino)borane is a precursor in the synthesis of water-soluble phosphines. The boranato group can be removed quantitatively under mild conditions.
- Day, Michael W.,Mohr, Bernhard,Grubbs, Robert H.
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Read Online
- Sequential Pd0- and PdII-Catalyzed Cyclizations: Enantioselective Heck and Nucleopalladation Reactions
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An enantioselective consecutive cyclization/coupling process, catalyzed by palladium is reported. Stereoinduction arises from an enantioselective carbopalladation, generating an intermediate which promotes a nucleopalladation step. The dual cyclization se
- Arora, Ramon,Bajohr, Jonathan,Lautens, Mark,Torelli, Alexa,Whyte, Andrew
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supporting information
p. 20231 - 20236
(2021/08/13)
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- The first IV group metal catalysts produced from these ligands and [...][...]
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Embodiments are directed to bis- and poly-phosphaguanidine compounds, and the metal-ligand complexes formed therefrom, wherein the metal complexes can be used as procatalysts in polyolefin polymerization. Formulas (I) (II) and (III).
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Paragraph 0182-0183
(2019/12/27)
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- N,N-BIS(2-DIALKYLPHOSPHINOETHYL)AMINE-BORANE COMPLEX AND PRODUCTION METHOD THEREFOR, AND METHOD FOR PRODUCING RUTHENIUM COMPLEX CONTAINING N,N-BIS(2-DIALKYLPHOSPHINOETHYL)AMINE AS LIGAND
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The purpose of the present invention is to provide an N,N-bis(2-dialkylphosphinoethyl)amine-borane complex which is a ruthenium complex that exhibits excellent catalytic activity in a hydrogenation reaction, etc., and a production method therefor, and a method for efficiently producing a ruthenium complex containing N,N-bis(2-dialkylphosphinoethyl)amine as a ligand. The present invention is capable of efficiently producing an amine-borane complex (3) by reacting an oxazolidinone compound (1) with a dialkylphosphine-borane compound (2) in the presence of a base. The present invention is also capable of efficiently producing a ruthenium complex (5) by reacting the amine-borane complex (3) with a ruthenium compound (4) in the presence of an amine. (In the formula, a solid line, a dashed line, B, C, H, L1-L3, LG, n, N, O, P, Ru, X, and R1-R10 are as defined in the description.)
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Paragraph 0106; 0115-0120
(2019/02/19)
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- TETRADENTATE LIGAND, AND PRODUCTION METHOD THEREFOR, SYNTHETIC INTERMEDIATE THEREOF, AND TRANSITION METAL COMPLEX THEREOF
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The present invention relates to: a compound as a ligand in a variety of catalytic organic synthetic reactions; a method for producing the compound; a synthetic intermediate of the compound; and a transition metal complex which has the compound as a ligand. The compound includes a compound represented by the following general formula (1A):
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Paragraph 0154-0156
(2019/05/15)
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- Phosphine- and amine-borane dehydrocoupling using a three-coordinate iron(II) β-diketiminate precatalyst
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Dehydrocoupling of phosphine- and amine-boranes is reported using an iron(II) β-diketiminate complex. Dehydrocoupling of amine-boranes is far more facile than the phosphine counterpart, the former proceeding at room temperature with 1 mol% iron precatalys
- Coles, Nathan T.,Mahon, Mary F.,Webster, Ruth L.
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supporting information
p. 2262 - 2268
(2017/06/19)
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- N-(PHOSPHINOALKYL)-N-(THIOALKYL)AMINE DERIVATIVE, METHOD FOR PRODUCING SAME, AND METAL COMPLEX THEREOF
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The purpose of the present invention is to provide: a ligand that is useful in a catalytic organic synthetic reaction; a method for producing said ligand; and a metal complex that is useful as a catalyst in an organic synthetic reaction. The present invention provides a compound represented by general formula (1A), a method for producing said compound, and a metal complex including said compound as a ligand. (In the formula, H, N, P, S, L, R1, R2, R3, Q1, and Q2 have the meaning as defined in the Description.)
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Paragraph 0259; 0260; 0261; 0262; 0263
(2017/09/02)
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- Stereoselective synthesis of o-bromo (or iodo)aryl P-chirogenic phosphines based on aryne chemistry
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The efficient synthesis of chiral or achiral tertiary phosphines bearing an o-bromo (or iodo)aryl substituent is described. The key step of this synthesis is based on the reaction of a secondary phosphine borane with the 1,2-dibromo (or diiodo)arene, owing to the formation in situ of an aryne species in the presence of n-butyllithium. When P-chirogenic secondary phosphine boranes were used, the corresponding o-halogeno-arylphosphine boranes were obtained without racemization in moderate to good yields and with ee up to 99%. The stereochemistry of the reaction, with complete retention of the configuration at the P atom, has been established by X-ray structures of P-chirogenic o-halogenophenyl phosphine borane complexes. The decomplexation of the borane was easily achieved without racemization using DABCO to obtain the free o-halogeno-arylphosphines in high yields.
- Bayardon, Jerome,Laureano, Hugo,Diemer, Vincent,Dutartre, Mathieu,Das, Utpal,Rousselin, Yoann,Henry, Jean-Christophe,Colobert, Francoise,Leroux, Frederic R.,Juge, Sylvain
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body text
p. 5759 - 5769
(2012/08/08)
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- Diphosphanes derived from phobane and phosphatrioxa-adamantane: Similarities, differences and anomalies
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The homodiphosphanes CgP-PCg (1) and PhobP-PPhob (2) and the heterodiphosphanes CgP-PPhob (3), CgP-PPh2 (4a), CgP-P(o-Tol) 2 (4b), CgP-PCy2 (4c), CgP-PtBu2 (4d), PhobP-PPh2 (5a), PhobP-P(o-Tol)2 (5b), PhobP-PCy2 (5c), PhobP-PtBu2 (5d) where CgP = 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-9-yl and PhobP = 9-phosphabicyclo[3.3.1]nonan-9-yl have been prepared from CgP(BH3)Li or PhobP(BH3)Li and the appropriate halophosphine. The formation of 1 is remarkably diastereoselective, with the major isomer (97% of the product) assigned to rac-1. Restricted rotation about the P-P bond of the bulky meso-1 is detected by variable temperature 31P NMR spectroscopy. Diphosphane 3 reacts with BH3 to give a mixture of CgP(BH3)-PPhob and CgP-PPhob(BH3) which was unexpected in view of the predicted much greater electron-richness of the PhobP site. Each of the diphosphanes was treated with dimethylacetylene dicarboxylate (DMAD) in order to determine their propensity for diphosphination. The homodiphosphanes 1 and 2 did not react with DMAD. The CgP-containing heterodiphosphanes 4a-d all added to DMAD to generate the corresponding cis alkenes CgPCH(CO2Me)CH(CO2Me)PR 2 (6a-d) which have been used in situ to form chelate complexes of the type [MCl2(diphos)] (7a-d) where M = Pd or Pt. The PhobP-containing heterodiphosphanes 3 and 5a-d react anomalously with DMAD and do not give the products of diphosphination. The X-ray crystal structures of the diphosphanes 2, 3, 4a, and 5a, the monoxide and dioxide of diphosphane 1, and the platinum chelate complex 7c have been determined and their structures are discussed.
- Dodds, Deborah L.,Floure, Joelle,Garland, Michael,Haddow, Mairi F.,Leonard, Thomas R.,McMullin, Claire L.,Orpen, A. Guy,Pringle, Paul G.
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experimental part
p. 7137 - 7146
(2011/09/13)
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- SULFONATED ORGANOPHOSPHINE COMPOUNDS AND USE THEREOF IN HYDROFORMYLATION PROCESSES
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A compound comprising a sulfonated triorganophosphine of formula R1R2PR3[SO3M)]n, wherein R1 and R2 are selected individually from alkyl, aralkyl, and alicyclic groups; wherein R
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Page/Page column 32
(2009/08/16)
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- Reduction of phosphinites, phosphinates, and related species with DIBAL-H
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Diisobutylaluminium hydride has been found to be an excellent reducing agent for phosphinites, phosphinates, and chlorophosphines. By performing reductions in situ, direct synthesis of secondary phosphine boranes from Grignard reagents has been achieved without isolation or purification of any intermediates. Georg Thieme Verlag Stuttgart.
- Busacca, Carl A.,Bartholomeyzik, Teresa,Cheekoori, Sreedhar,Raju, Ravinder,Eriksson, Magnus,Kapadia, Suresh,Saha, Anjan,Zeng, Xingzhong,Senanayake, Chris H.
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experimental part
p. 287 - 291
(2009/07/01)
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- Transition metal-catalyzed dissociation of phosphine-gallane adducts: Isolation of mechanistic model complexes and heterogeneous catalyst poisoning studies
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Attempts to induce the catalytic dehydrocoupling of the phosphine-gallane adduct Cy2PH·GaH3 (Cy = cyclohexyl) (1) by treatment with ca. 5 mol % of either the Rh(I) complex [{Rh(μ-Cl)(1,5-cod)} 2] (cod = cyclooctadiene) or the Rh(0) species Rh/Al 2O3 and [Oct4N]Cl-stabilized colloidal Rh led to catalytic P-Ga bond cleavage to generate the phosphine, H2, and Ga metal. Interestingly, subsequent treatment of the reaction mixtures with Me2NH·BH3 failed to lead to the formation of [Me2N-BH2]2 via Rh-catalyzed dehydrocoupling, which suggested that catalyst deactivation was taking place. Poisoning studies involving the treatment of the active Rh(0) catalyst with Cy2PH, PMe3, or GaH3·OEt2 showed that deactivation indeed occurred as the dehydrocoupling of Me2NH· BH3 either dramatically decreased in rate or did not take place at all. The X-ray photoelectron spectroscopy analysis of colloidal Rh(0) that had been treated with Cy2PH and PMe3 confirmed the presence of phosphorus on the catalyst surface in each case, consistent with catalyst poisoning via phosphine ligation. A mechanism for the Rh-catalyzed P-Ga bond cleavage reaction of 1 and Me3P·GaH3 (2) is proposed and involves the initial reaction of Ga-H bonds with the Rh colloid surface, which weakens and ultimately breaks the P-Ga bond. The reasonable nature of this mechanism is supported by a model reaction between the zerovalent group 9 complex Co2(CO)8 and 2 which afforded Me 3P·Ga[Co(CO)4]3 (3). Consistent with the elongated and thus weakened P-Ga bond in 3, solutions of this species in Et2O subsequently form the known complex [(Me3P)Co(CO) 3]2 (4) and Ga metal after 4 h at 25°C.
- Clark, Timothy J.,Jaska, Cory A.,Turak, Ayse,Lough, Alan J.,Lu, Zheng-Hong,Manners, Ian
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p. 7394 - 7402
(2008/10/09)
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- Preparation of secondary phosphines
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The present invention relates to a method for preparing di-α-chiral and achiral di(sec. alkyl)phosphines of general formula Ia or Ib which is characterized in that sulfonates of general formula IIa or IIc or sulfates of general formula IIb or IId, are rea
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Page/Page column 7
(2010/11/29)
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- PROCESS FOR PRODUCTION OF PHOSPHINE-BORANE COMPLEXES
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A process for the production of phosphine-borane complexes represented by the general formula: or salts thereof: [wherein R1, R2 and R3 are each independently a hydrogen atom, a halogen atom, an optionally substituted alky
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Page/Page column 9
(2008/06/13)
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- A highly efficient general synthesis of phosphine-borane complexes
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A general synthesis of phosphine-borane complexes proceeding in high yield in a safe, green process from borane generated in situ from sodium borohydride is described. The procedure also allows simultaneous carbonyl reduction and phosphine-borane formation on air-sensitive bulky phosphine derivatives.
- McNulty, James,Zhou, Yuehui
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p. 407 - 409
(2007/10/03)
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- Synthesis of water-soluble, aliphatic phosphines and their application to well-defined ruthenium olefin metathesis catalysts
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Water-soluble aliphatic phosphines Cy2P(CH2)2N(CH3)3 +Cl- (14), Cy2P[4-(N,N-dimethyl-piperidinium)]+Cl- (15), Cy2P(CH2)2SO3-Na + (16), and CyP[(CH2)2N(CH3)3+Cl -]2 (17) (Cy = cyclohexyl) were prepared from air-stable, borane-protected precursors. Spectroscopic investigations of corresponding Pd(PR3)2Cl2 complexes were used to estimate the steric parameters of these new phosphines. Spectroscopic investigation of Ni(CO)3PR3 complexes of the new phosphines indicated that phosphines bearing quaternary amine functionalities were less electron donating than tricyclohexylphosphine, while the presence of a sulfonate group increased phosphine electron donation. Cationic phosphines 14 and 15 were used to synthesize water-soluble ruthenium carbene complexes of the type (Cy2PR)2Cl2Ru=CHPh. These complexes initiate the ring-opening metathesis polymerization (ROMP) of functionalized 7-oxanorbornenes in water, methanol, and aqueous emulsions.
- Mohr, Bernhard,Lynn, David M.,Grubbs, Robert H.
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p. 4317 - 4325
(2008/10/08)
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