Process for catalytic addition of nucleophiles to alkynes or all

Details Process for catalytic addition of nucleophiles to alkynes or all Process for catalytic addition of nucleophiles to alkynes or all

1998-06-15

2000-03-14

Geist, Gary

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

549430, 568409, 568594, 568672, 568678, 568690, 568695, 568892, 568898, C07D31912

Patent

active

060374829

DESCRIPTION:

BRIEF SUMMARY
DESCRIPTION

The present invention relates to a process for the addition of nucleophiles to alkynes and allenes in the presence of a wholly or partly ionized complex of univalent gold applicable to a wide range of alkynes and allenes.
The addition of nucleophiles to alkynes is catalyzed by acids, bases or transition metal complexes (cf. Houben-Weyl, Methoden der organischen Chemie, Vol. 6/3, p. 233, p. 90, Vol. 5/2a, p. 738, Vol. 6/1d, p. 136 and Vol. 7/a, p. 816).
The acid catalysis is usually restricted to the addition of nucleophiles to activated, electron-rich alkynes (such as acetylene ethers, R--C.tbd.C--OR', acetylene thioethers, R--C.tbd.C--SR' and acetyleneamines, --C.tbd.C--NR'.sub.2).
Alcohols can be added to unactivated alkynes by base catalysis (in the presence of KOH or alcoholate). This is the method of choice for the monoaddition of alcohols to alkynes to form enol ethers.
The addition of nucleophiles to alkynes is also catalyzed by transition metal complexes. Generally, they are complexes of metals of groups 11 and 12 (according to the currently applicable IUPAC nomenclature of inorganic chemistry). Rhodium, ruthenium, palladium and platinum catalysts have also been used in individual cases.
According to J. S. Reichert, H. H. Bailey, J. A. Nieuwland, J. Am. Chem. Soc., 45 (1923), 1552, and G. F. Hennion, J. A. Nieuwland, J. Am. Chem. Soc., 57 (1935), 2006, mercury(II) compounds, usually in combination with a Lewis and a Brbnsted acid, are the most active catalysts for the addition of nucleophiles to alkynes. Such Hg(II) catalysts can be used to add water, alcohols and carboxylic acids to alkynes. These catalysts have very general utility, but their scope of application is limited by the toxicity of mercury and by the relatively low turnover numbers (<500), ie. the ratio of the number of moles of product formed per mole of catalyst.
W. Reppe, Ann., 601 (1956), 81, describes zinc(II) and cadmium(II) compounds for use as catalysts for the addition of carboxylic acids and phenols to alkynes.
Gold(III) compounds such as sodium tetrachloroaurate (NaAuCl.sub.4) have hitherto been described for use as catalysts for the addition of water or alcohols to alkynes only once (Y. Fukuda, K. Utimoto, J. Org. Chem., 56 (1991), 3729).
Gold(I) compounds have evidently hitherto not been used as ctalysts for the addition of nucleophiles to alkynes.
As can be seen from the description of the background art, there are numerous existing processes for the addition of nucleophiles to alkynes, but they all have a limited range of applications. The hitherto preferred mercury catalysts, in particular, have the disadvantage of toxicity and relatively low turnover numbers, so that a high catalyst consumption had to be tolerated or appreciable amounts of byproducts were formed.
It is an object of the present invention to propose a universally useful catalytic process for the addition of nucleophilic agents to alkynes or allenes and, more particularly such a process as does not have the disadvantages described and which even makes possible the addition of weak nucleophiles and the addition to unactivated alkynes.
We have found that this object is achieved according to the invention by a process for the catalytic addition of nucleophilic agents to alkynes or allenes to form alkenes substituted by the nucleophile which may further react with the nucleophile and/or isomerize, which comprises using a catalyst comprising a wholly or partly ionized complex of univalent gold.
Since the complexes have to be at least partly present in ionized form, it is assumed that the catalytic effect is due to a complex cation of the formula 1 ##STR1## and where R.sup.1, R.sup.2 and R.sup.3 independently of the others represent substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, heteroaromatic or araliphatic radicals having from 1 to 30 carbon atoms which may be bridged and may optionally be attached to E via an oxygen atom or via a nitrogen atom, substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, heteroaromatic

REFERENCES:
Journal of Organic Chemistry by Fuduka et al. 56 pp. 3729-3731 1991.
JAPIO1992-095039 abs of JP04095039 by Yukitoshi.

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