Π-allyltricarbonyliron Lactone Complexes Research Articles

1,5-Asymmetric induction of chirality: diastereoselective addition of organoaluminium reagents and allylstannanes into aldehyde groups in the side-chain of π-allyltricarbonyliron lactone complexes

π-Allyltricarbonyliron lactone complex 5, bearing an aldehyde group in the side-chain, can be easily prepared from commercially available (2E,4E)-ethyl hexadienoate and reacts with organoaluminium and allylstannane nucleophiles to afford secondary alcohols. In analogy with the corresponding ketone-substituted complexes, the lactone tether acts via the Fe(CO)3 moiety as a source of asymmetric induction. The levels of diastereoselectivity are generally reduced, however, compared with those obtained using ketone complexes. This can be attributed, at least in part, to the carbonyl appendage adopting both s-cis and s-trans conformations. The level of 1,5-asymmetric induction is strongly dependent upon the nature of the nucleophile in the case of the organoaluminium reactions and upon the reaction temperature in the case of BF3-mediated addition of allylstannanes into the aldehyde group.

Synthesis of β-dimorphecolic acid exploiting highly stereoselective reduction of a side-chain carbonyl group in a π-allyltricarbonyliron lactone complex

S. V. Ley and G. Meek, J. Chem. Soc., Perkin Trans. 1, 1997, 1125 DOI: 10.1039/A607376J

1,5-Asymmetric induction of chirality: highly diastereoselective synthesis of homoallylic tertiary alcohols by the Lewis acid-mediated addition of allylstannanes into ketones in the side-chain of π-allyltricarbonyliron lactone complexes

Allylstannanes add into ketone groups in the side-chain of π-allyltricarbonyliron lactone complexes to afford the corresponding homoallylic tertiary alcohol complexes with very high levels of diastereocontrol. The reaction provides an example of 1,5-asymmetric induction of chirality with the lactone tether acting as the source of induction. The endo addition complexes can be converted into (E,E)-dienes bearing an α tertiary alcohol chiral centre in two steps proceeding via the η4-dienetricarbonyliron complexes. No loss of enantio- or diastereo-purity is observed during decomplexation.

1,5-Asymmetric induction of chirality: highly diastereoselective addition reactions of organoaluminium reagents into ketone groups in the side-chain of π-allyltricarbonyliron lactone complexes

The utility of π-allyltricarbonyliron lactone complexes has been extended to include their use as chiral auxiliaries. Organoaluminium reagents add into ketone groups positioned in the side-chain of the allyl ligand to afford the corresponding tertiary alcohol complexes in good to excellent yield and with excellent diastereocontrol. Enantiomerically enriched complexes can be synthesised using the Sharpless asymmetric epoxidation protocol as the source of chirality. Addition products derived from endo ketones can be converted into the corresponding (E,E)-η4-dienetricarbonyliron complexes upon treatment with barium hydroxide solution without loss of diastereo- or enantio-purity.

Diastereoselective additions to aldehyde groups in the side-chain of π-allyltricarbonyliron lactone complexes

π-Allyltricarbonyliron lactone complexes containing aldehyde groups adjacent to the allyl system undergo addition reactions with a variety of organoaluminium reagents in moderate to excellent diastereoselectively.

Diastereoselective addition reactions of allylstannanes to carbonyl groups in the side-chain of π-allyltricarbonyliron lactone complexes

Lewis acid-mediated addition of allylstannanes to ketones adjacent to the allyl system of π-allyltricarbonyliron lactone complexes generates the corresponding homoallylic tertiary alcohols with excellent diastereocontrol.

Synthesis of β-dimorphecolic acid exploiting highly stereoselective reduction of a side-chain carbonyl group in a π-allyltricarbonyliron lactone complex

A highly Stereoselective synthesis of β-dimorphecolic acid is accomplished utilising a π-allyltricarbonyliron lactone complex 3 to control the formation of all the stereochemical features of the natural product.

Diastereoselective addition reactions to carbonyl groups in the side-chain of π-allytricarbonyliron lactone complexes

Organoaluminium reagents add in a highly diastereoselective fashion to carbonyl groups adjacent to the allyl system of π-allyltricarbonyliron lactone complexes.

Total synthesis of the ionophore antibiotic CP-61,405 (routiennocin)

The total synthesis of the spiroketal ionophore antibiotic routiennocin 1 (CP-61,405) employing π-allyltricarbonyl iron lactone complexes is described. These complexes were used as precursors for the preparation of substituted 2-phenylsulphonyl pyrans which, in turn, were coupled with iodoacetonides to afford spiroketals. Elaboration of the spiroketals by tetra- n-propylammonium perruthenate (TPAP) oxidation and coupling with 2-lithio-1-[β-(trimethylsilyl)ethoxymethyl] pyrrole followed by further oxidation, deprotection, oxidation and benzoxazole formation afforded the natural product. The preparation of the amino phenol fragment necessary for benzoxazole formation involved a novel amination procedure using benzeneselenenic anhydride and hexamethyldisilazane followed by samarium diiodide reduction.

The use of π-allyltricarbonyliron lactone complexes in the synthesis of the β-lactone esterase inhibitor (−)-valilactone.

A concise synthesis of the β-lactone esterase inhibitor valilactone (1) is reported. This synthesis employs the stereoselctive preparation of a π-allyltricarbonyliron lactone complex (7) that on oxidation with ceric ammonium nitrate, affords an appropriately substituted β-lactone (9) which was transformed to (1).

Synthesis of the β-lactone esterase inhibitor valilactone using π-allyltricarbonyliron lactone complexes.

Synthesis of the esterase inhibitor valilactone (1) is reported employing the oxidation of π-allyltricarbonyliron lactone complexes with ceric ammonium nitrate to afford the inherent β-lactone ring.

Total Synthesis of Avermectin B1a: Synthesis of the CarbohydrateBis-Oleandrose Fragment and Coupling to the Avermectin B1a Aglycone

A synthesis of the bis-oleandrose fragment of avermectin B1a (1) is described, involving π-allyl tricarbonyliron lactone complexes as key synthetic intermediates. Final glycosidation to the aglycone employed the use of an imidazolylthiocarbonyl glycoside, to conclude the total synthesis of avermectin B1a.

Assessment of butene-1,4-diols as starting materials for the preparation of π-Allyltricarbonyliron complexes

This work assesses the use of butene-1,4-diols as starting materials for the synthesis of π-allyltricarbonyliron lactone complexes. It has been shown that substituents, and the use of Lewis acids, mainly ZnBr 2, in reactions with Fe 2(co) 9 in benzene under ultrasonic conditions or in THF, greatly influence the yield and the product distribution.

Alkenylcyclic Sulphites as Novel Precursors for the Preparation of π-Allyltricarbonyliron Lactone Complexes

Substituted 3-butene-1,2-diol sulphites react with diiron nonacarbonyl in benzene at room temperature under ultrasonication to afford good yields of π-allyltricarbonyliron lactone complexes.

ChemInform Abstract: NATURAL PRODUCT SYNTHESIS VIA Π‐ALLYLTRICARBONYLIRON LACTONE COMPLEXES

Chemischer InformationsdienstVolume 16, Issue 29 Reviews ChemInform Abstract: NATURAL PRODUCT SYNTHESIS VIA Π-ALLYLTRICARBONYLIRON LACTONE COMPLEXES G. D. ANNIS, G. D. ANNISSearch for more papers by this authorE. M. HEBBLETHWAITE, E. M. HEBBLETHWAITESearch for more papers by this authorS. T. HODGSON, S. T. HODGSONSearch for more papers by this authorA. M. HORTON, A. M. HORTONSearch for more papers by this authorD. M. HOLLINSHEAD, D. M. HOLLINSHEADSearch for more papers by this authorS. V. LEY, S. V. LEYSearch for more papers by this authorC. R. SELF, C. R. SELFSearch for more papers by this authorR. SIVARAMAKRISHNAN, R. SIVARAMAKRISHNANSearch for more papers by this author G. D. ANNIS, G. D. ANNISSearch for more papers by this authorE. M. HEBBLETHWAITE, E. M. HEBBLETHWAITESearch for more papers by this authorS. T. HODGSON, S. T. HODGSONSearch for more papers by this authorA. M. HORTON, A. M. HORTONSearch for more papers by this authorD. M. HOLLINSHEAD, D. M. HOLLINSHEADSearch for more papers by this authorS. V. LEY, S. V. LEYSearch for more papers by this authorC. R. SELF, C. R. SELFSearch for more papers by this authorR. SIVARAMAKRISHNAN, R. SIVARAMAKRISHNANSearch for more papers by this author First published: July 23, 1985 https://doi.org/10.1002/chin.198529392AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume16, Issue29July 23, 1985 RelatedInformation

Natural product synthesis using π-allyltricarbonyliron lactone complexes: Synthesis of parasorbic acid, the carpenter bee pheromone and malyngolide

Preparation of three δ-lactonic natural products, parasorbic acid, the carpenter bee pheromone and malyngolide has been achieved from π-allyltricarbonyliron lactone complexes as the key synthetic intermediates.

Synthesis of the β-lactam antibiotic (+)- thienamycin via an intermediate π-allyltricarbonyliron lactone complex

The π-allyltricarbonyliron lactone complex ( 7), formed by reaction of E-1,2-epoxy-2-methyl-6,6-dimethoxyhex-3-ene( 5) with co-ordinatively unsaturated iron carbonyl species, was reacted with benzylamine to give a lactam complex ( 8) by an S N'-like mechanism. This complex upon oxidation with Ce( IV) afforded cis-3-isopropenyl-4-[(2',2'-dim ( 9) which was chemically modified into trans-3-(1'-hydroxyethyl)-4-[(2',2-dimethoxy)ethyl] azetidin-2-one ( 13), a key intermediate previously used in the synthesis of the antibiotic thienamycin. Similar reaction with ( S)-(-)-α-methylbenzylamine afforded a separable mixture of diastereoisomeric iron lactam complexes ( 16 and 17). These complexes could be individually converted to the corresponding optically active β-lactam derivatives ( 27 and 28) and, hence, are precursors for the synthesis of either natural (+)-thienamycin or unnatural (-)-thienamycin.

π-Allyltricarbonyliron lactone complexes in synthesis: application to the synthesis of the β-lactam antibiotic (+)-thienamycin

Synthesis of an enantiomerically pure β-lactam intermediate used in the preparation of the antibiotic (+)-thienamycin is described, by suitable elaboration of a functionalised π-allyltricarbonyliron complex.

Fe 2(co)g in tetrahydrofuran or under sonochemical conditions as convenient practical routes to π-allyltricarbonyliron lactone complexes

A series of alkenyl epoxides were converted into their corresponding π-allyltricarbonyliron lactone complexes by either treatment with tetrahydrofuran solutions of Fe 2(CO) 9 at room temperature, or in hydrocarbon solvents with Fe 2(CO) 9 under ultrasonification conditions. The new routes constitute convenient practical alternatives to presently existing methodology.

Synthesis of β-lactams from π-allyltricarbonyliron (lactone) complexes

Several π-allyltricarbonyliron (lactone) complexes have been treated with an excess of benzylamine in the presence of Lewis acids to afford the corresponding lactam complexes by an SN2′-like process. These lactam complexes were oxidised in good yield with ceric ammonium nitrate to provide a novel route to a variety of β-lactam compounds. Simple chemical transformations of the resulting β-lactams have been investigated; these include the conversion of the vinyl and isopropenyl side chains into hydroxyethyl substituents and the reductive removal of benzyl groups to afford the parent NH β-lactams.