Diethylaluminium cyanide

The viabihty of this synthetic approach to the introduction of a carboxylic acid fimction at C2 has been demonstrated in two ways. Following lithium diphenylcuprate addition to 564, the newly introduced phenyl group is subsequently degraded by ozonolysis to provide 567. Alternatively, reaction of 564 with diethylaluminium cyanide in toluene gives 568 which is also conveniently transformed into 567... 

S. Watanabe, J. Kavai, and M. Bobek, Cyano sugars synthesis by opening of an epoxide ring in pentofuranosides with diethylaluminium cyanide, J. Carbohydr. Chem., 14 (1995) 685-701. 

Hydrocyanation. Although 2-carbomethoxy-2-cyclopentene-l-one (2) is prone to polymerization, it reacts smoothly with diethylaluminium cyanide to give the adduct 3. This product has the carbon skeleton of sarkomycin (7), an antibiotic active against ascites-type tumors. Selective manipulation of the functionaTgroups resulted in the first regiospecific synthesis of 7. ... 

Diethoxy-l-propene, 158 N,N-Diethylacetamide, 220 Diethylaluminium cyanide, 158-159, 328 N,N-Diethylaminoacetonitrile, 159 Diethylaminodichloroborane, 63 N,N-Diethylaminopropyne, 164-165 Diethylaminosulfur trinuoride, 149, 224 Diethyl azodicarboxylate, 160, 423 Diethyl chlorophosphatc, 1 Diethyl(2-chloro-l, 1,2-trifluoroethyl)amine,... 

Conjugate hydrocyanation of oc -unsaturated carboxylic esters, acid chlorides, and acyl cyanides, is effected by reaction with diethylaluminium cyanide [e.g. (128) — (129)]. The acid chloride and cyanide are the most reactive. A double conjugate addition of nitromethane with a 2-methylene-4-en-3-one (130) gave a... 

C-cyano-3 -deoxy-P-D-ffcr o and erythro nucleosides 47 (63%) and 31 (25%). Related openings of 2, 3 -anhydro-P-D-lyxofuranosyl nucleosides with sodium cyanide [84] and with diethylaluminium cyanide [85] to afford 3 -C-cyano-3 -deoxy-P-D-arabinofuranosyl derivatives of adenine, uracil, thymine and isocytosine have been described. 

Diethylaluminium cyanide p-Hydroxynitriles from oxido compds. 

The smooth cleavage of steroidal epoxides to give trans diaxial /3-hydroxy-nitiiles has been accomplished by the use of the powerful hydrocyanation reagents, diethylaluminium cyanide (Et2AlCN) and hydrogen cyanide-triethyl-aluminium (HCN—Etj Al). 

Diethylaluminium cyanide is a valuable reagent for the conjugate addition of HCN to o , 3-unsaturated carboxylic acid derivatives [120]. Steroidal conjugate esters are somewhat resistant to HCN addition even with this powerful reagent and optimum yields of only 36-50% were obtained. With aj3-unsaturated acid chlorides and acid cyanides, however, the reaction proceeds smoothly in toluene at room temperature and, after hydrolysis the 0-cyanoacid was obtained in 71—73% yield. Conjugated steroidal thiocarboxylic S-esters react under similar conditions to give the product in yields of 85-87%. 

In the catalytic enantioselective Strecker reaction, chiral aluminium complexes, especially aluminium-salen-based catalysts and aluminium-binaphthol-based catalysts have been widely used, and great achievements have been obtained. In 2010, the Li group reported a highly enantioselective Strecker reaction of achiral IV-phosphonyl imines by using primary free L-phenglycine 42 as the catalyst and diethylaluminium cyanide as the nucleophile. This work also presented the novel use of nonvolatile and inexpensive diethylaluminium cyanide in asymmetric catalysis (Scheme 19.51). ... 

Scheme 19.51 Asymmetric Strecker reaction with diethylaluminium cyanide as the nucleophile.

The 2,3-unsaturated glycosyl cyanides obtainable from glycal derivatives are of appreciable interest as synthetic intermediates and have been produced by use of trimethylsilyl cyanide in nitromethane with boron trifluoride etherate as catalyst [40]. While under these conditions the anomeric cyanides are obtained from tri-O-acetyl-D-glucal in an a/p ratio of 1.4 1, the product formed with dichloromethane as solvent contains only the a-isomer [41]. Similar results are obtained by use of the Lewis acid diethylaluminium cyanide which, in benzene at room temperature, affords the 2,3-unsaturated glycosyl cyanides from tri-O-acetyl-D-... 

A mixture of the P-D-mannofuranosyl isonitrile (46 76%) and nitrile (47 8%) and small proportions of their a-anomers was obtained on treatment of the corresponding glycosyl fluoride with diethylaluminium cyanide. Similar results were obtained with the l,2 4,6-di-0-isopropylidene-D-... 

Reaction of trimethylsilyl cyanide with the o-glyceraldehyde-derived nitrone 70 gave the o-tAreo-adduct 71 (Scheme 12), whereas diethylaluminium cyanide gave a mixture of D-erythro- and D-tAreo-adducts in a 3 7 ratio. ... 

An improved synthesis of 3-cyano-3-deoxy- and 3-deoxy-3-formyl-hex-2-eno-pyranosides has been described. Thus treating methyl 2,3-anhydro-4,6-0-benzyl-idene-a-D-galactopyranoside with diethylaluminium cyanide (epoxide ring opening with CN) then elimination of water with diisopropylamine, lithium perchlorate and tosyl chloride afforded 39 which on reduction with DIBAL gave 40.34... 

Full details on the preparation of urethane derivatives of 3,4-di-O-benzyl-l,2,5,6-tetradeoxy-l,2 5,6-diimino-L-iditol from D-mannitol as well as the 3,4-dideoxy-L- Areo compounds 24 (R = C02 Bu or COiBn), from a hex-3-enitol, have been reported. (See Vol. 28, p. 230, ref. 66 for an earlier report). In both cases l,6-diamino-l,6-dideoxy-2,5-anhydroalditols were minor by-products. V-Boc-L-/V/o-l,2 5,6-bis-aziridino derivatives have proved to be versatile intermediates for the preparation of imino-alditols. For example, treatment of the 3,4-di-O-benzyl compound with diethylaluminium cyanide affords a 1 2 mixture of pyrrolidine 25 piperidine 26, and with dilithium tetrabromonickelate (Li2NiBr4) gives bromo-derivative 27 from which displacement of bromide allows further functionalization. ... 

Trapping of the initially formed aluminium enolate from a,/8-unsaturated ketones and diethylaluminium cyanide, with chlorotrimethylsilane-pyridine yields the corresponding silylenol ethers (35), which can be alkylated or phenyl-sulphenylated (Scheme 22). ... 

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