36677-67-5Relevant academic research and scientific papers
Mechanism and scope of the cyanide-catalyzed cross silyl benzoin reaction
Linghu, Xin,Bausch, Cory C.,Johnson, Jeffrey S.
, p. 1833 - 1840 (2007/10/03)
In this work, cross silyl benzoin addition reactions between acylsilanes (1) and aldehydes (2) catalyzed by metal cyanides are described. Unsymmetrical aryl-, heteroaryl-, and alkyl-substituted benzoin adducts can be generated in moderate to excellent yie
Photochemical synthesis of highly functionalized cyclopropyl ketones
Wessig, Pablo,Muehling, Olaf
, p. 865 - 893 (2007/10/03)
A series of di- and trisubstituted cyclopropyl ketones 11 were prepared by irradiation of ketones 3 and 5, which bear a leaving group adjacent to the carbonyl C-atom. The required ketones 3 could be easily synthesized either by functionalization of ketones 1 with a hypervalent iodine reagent, 2, or by O-sulfonylation of α-hydroxy ketones 7. The nitrates 5 were obtained by treatment of the corresponding α-bromo ketones with AgNO3. The irradiation of 3 and 5 must be performed in the presence of an acid scavenger (1-methyl-1H-imidazole) to obtain the cyclopropanes 11 in good yields. The synthetic efficiency of the method was, among other things, demonstrated by the preparation of a highly strained bicyclo[2.1.0]pentane 11i in good yield. The mechanism of the photochemical cyclization was investigated by means of photokinetic measurements, as well as by quantum-chemical calculations. It was shown that the presence of the leaving group substantially influences all steps of the photochemical reaction cascade. The X-ray crystal structures of 11j and exo-11k were also determined.
A new photochemical route to cyclopropanes
Wessig, Pablo,Muehling, Olaf
, p. 1064 - 1065 (2007/10/03)
Especially highly substituted cyclopropanes can be produced with a new photochemical approach. Starting with aromatic ketones that bear a leaving group adjacent to the carbonyl carbon atom, photolysis leads to the formation of 1,3-diradicals, which efficiently cyclize to cyclopropanes (see scheme; Ms=MeSO2).
Conversion of ketone trimethylsilylcyanohydrins to several types of compounds
Ohta,Yamashita,Arita,Kajiura,Kawasaki,Noda,Izumi
, p. 1294 - 1301 (2007/10/02)
Cyclic ketone O-trimethylsilylcyanohydrins (2) were prepared and converted to various compounds: α-hydroxyketones (3), dehydroxylated ketones (4), α,β-unsaturated ketones (9), tricyclic ketones (10), 1-ethoxycarbonyl-4- phenyl-1,2,4a,5,6,7,8,8a-octahydro-2-naphthalenone (13), 1- phenylperhydroisocoumarin (18) and 1,2,3,4,4a,10,11,11a-octahydro-5h- benzo[a,d]cyclohepten-10-one (20).
ADDITION OF GRIGNARD REAGENTS TO O-TRIMETHYLSILYLATED CYANOHYDRINS: SYNTHESIS OF ACYLOINS
Krepski, Larry R.,Heilmann, Steven M.,Rasmussen, Jerald K.
, p. 4075 - 4078 (2007/10/02)
Grignard reagents have been found to react readily with O-trimethylsilylated cyanohydrins to afford, after acid hydrolysis of intermediates, good yields of acyloins.
