Carbohydrate-derived phosphines

Some phosphines are easily soluble in water due to their strong hydrogen-bonding capacity. Representatives of these ligands are l,3,5-triaza-7-phosphaadaman-tane (pta), the polyoxyethylene-substituted and the carbohydrate-derived phosphines. A detailed compilation of water-soluble phosphines (together with the known solubilities) can be found in [4],... 

Figure JO. Macromolecular and carbohydrate-derived phosphine ligands...

Many applications of sodium and potassium organophosphides have been reported in the past year. The reaction of sodium diphenylphosphide with tosylates has been employed in the synthesis of steroidal phosphines. This reagent has also been used in the synthesis of a range of carbohydrate-derived phosphines, and in the synthesis of the phosphine (26), which can be linked to a silica support by treatment with acid. The reaction of sodium diphenylphosphide with o-difluorobenzene affords a convenient, one-pot synthesis of o-bis(diphenyl-phosphino)benzene. Sodium dimethylphosphide has been used to convert... 

The homo- and cross-addition of alkenes catalyzed by a transition-metal provided another economical way of forming C-C bonds.155 These reactions are carried out by using nickel, palladium, or ruthenium phosphine complexes to yield vinylarenes and some can occur in aqueous media. By using carbohydrate-derived ligands, asymmetric hydrovinylations can be carried out in aqueous conditions.156... 

A new procedure for cleaving allyloxycarbonates using Pd(0), formed in situ from Pd(OAc)2 and trisodium tris(m-sulfophenyl)phosphine, with sodium azide as allyl scavenger, has been applied to a number of carbohydrate derivatives. ... 

Nickel-catalyzed ketone and aldehyde hydrosilylations have been developed with well-defined Ni(II) hydrides using phosphine anilide ligands (Scheme 3-84). This process is tolerant of a variety of functional groups including aryl halides. In mechanistically distinct processes, nickel(O) complexes of NHCs were shown to catalyze ketone hydrosilylations using carbohydrate-derived silanes in a process that allows reductive glycosylations of ketones. Chemoselectivity of the latter method was optimal in the presence of Ti(OR)4 additives. 

Given the efficiency and utility of the butadiene hydrocyanation process, its potential in more complex settings is underused. Whereas the range of applications has mostly been limited to simple substrates, several important developments in reaction scope and as5mimetric induction have appeared. For example, carbohydrate-derived bis-phosphine ligands allowed efficient asymmetric hydrocyanations of... 

Tris(diethylamino)phosphine/pyridine Bicyclic phosphites Carbohydrate derivs. 

In general, the chiral ligands are water-soluble variants of those already studied in purely organic solvents (e.g., the sulfonated chiraphos, A, cyclobutane-diop, C, BDPP, F, MeOBIPHEP-TS, Q, BIFAPS, R and the quaternary ammonium derivatives of diop, D, BDPP, E). Solubility in water could also be achieved by attaching the parent phosphine molecule to a water-soluble polymer (J, M, P). The chiral phosphinites and phosphines derived from carbohydrates (e.g., K and L) have intrinsic solubility in water. During studies of one-phase... 

Biological chemistry and its needs increasingly dominate the phosphorus(v) acids area and the majority of novel results relate to compounds derived from phosphonic and phosphinic, rather than phosphoric acids. Numbers of studies of compounds related to inositol and to carbohydrates continue to appear, although few contain truly novel results. Phosphorus-containing analogues of amino acids... 

Some preliminary results were obtained concerning the asymmetric Pd-cata-lyzed alkylation of l,3-diphenyl-2-propenyl acetate in water or in an aqueous/or-ganic biphasic medium, using as the chemical ligands phosphines derived from carbohydrates (ee up to 85%) [32], amphiphilic resin-supported MOP and P,N-che-lating ligands (ee up to 98%) [33, 34], or BINAP in the presence of surfactants (ee up to 92%) [35],... 

Water-Soluble Photoinitiators Due to their polar structure, hydrophilic or water-soluble photoinitiators derived from basic structures (hydroxyl alkyl ketones [92] such as the one in (10.41), phosphine oxides [93,94], etc.) or modified compounds (e.g., by carbohydrates [95]) are usable in water-based matrices (water-soluble monomers and aqueous dispersions). Their reactivity has been studied [96,97]. 

Miscellaneous Systems Many systems have been mentioned [li,m,2i] acyloxy and acylsilyl phosphine oxides, phosphine sulfides, cyclic compounds, benzoyloxa-ziridine derivatives, dibenzoylmethane derivatives, triazene and pentaazadiene moiety containing compounds. New developments include benzyl benzoin benzyl ethers [112], dithiocarbamates [113], ketoamides [114], phosphonates [115], bromo-acetylpyrene [116], alkylimides [117], aryloxy naphthalene [118], oligosilanes [119], bisphosphine sulfides [120], sulfamic esters of benzoin ethers [121], sulfur [122], or carbohydrate [123] containing compounds. 

Lithiophosphide reagents have also found application in the synthesis of a range of chiral phosphines based on carbohydrate systems, e.g., (43), the key step being nucleophilic ring-opening of epoxide derivatives with lithium diphenyl-phosphide. A lithiophosphide-tosylate route has been used in the synthesis of the carbohydrate-based diphosphine (44). Conjugate addition of lithium diphenyl-phosphide to a,P-unsaturated carboxylic esters is the key step in the synthesis of... 

The more customary Michaelis-Becker reaction has not been widely adopted for the synthesis of oxoalkyl-phosphonic or -phosphinic esters, and only isolated examples are to be noted, sometimes in combination with a Michaelis-Arbuzov step. The steps in Scheme 51 were adopted to furnish acylphosphorus(V) derivatives of a carbohydrate nucleus (R = a carbohydrate moiety), and a similar sequence (Scheme 52) starts with bis(trimethylsilyl) hypophosphite and can provide novel bis(l-oxoalkyl)phosphinic acids, e.g.53r ... 

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