117679-60-4Relevant academic research and scientific papers
Thermolysis of 7-(Acylamino)-7-azabenzonorbornadienes and 1-(Acylamino)aziridines. Generation and Trapping of Monosubstituted Azamines
Carpino, Louis A.,Padykula, Robert E.,Lee, Sung-Nung,Han, Grace Y.,Kirkley, Robert K.
, p. 6047 - 6053 (2007/10/02)
The thermolysis of 7-carbonyl>amino>- and 7-(benzoylamino)-7-azabenzonorbornadienes (2a and 2 b) in various solvents has been studied.In the absence of an olefinic trapping agent the major products other than naphthalene are the corresponding hydrazides 6a,b.In cyclohexene as solvent, the aziridines 7a,b are formed, suggesting that the azamine 3 is ejected and captured by the olefin.For the olefin cis-4-methyl-2-pentene the reaction occurs with greater than 95percent stereoselectivity in further agreement with a labile azamine intermediate.Thisrepresents the first demonstration that a monosubstituted azamine has independent existence and reacts with olefin faster than it undergoes 1,2-hydrogen shift.Synthesis of the related 7-phthalimido-7-azabenzonorbornadiene (17) was achieved via rearrangement of the corresponding isophthalimide derivative 18, which could be obtained by reaction of phthaloyl chloride with hydrazine 1.Thermolysis of 17 caused fragmentation to naphthalene and phthaloylazamine 13 as shown by trapping of the latter.This reaction represents a new thermal source of transient species 13.For synthetic purposes more practical intermediates for the generation of 3 are the aziridines 21 and 22.The cis analogues (23) of 21 proved to be relatively stable thermally.A new route is presented for the synthesis of 1-amino-cis-2,3-diphenylaziridine.
The Mechanism of Asymmetric Hydrogenation. Chiral Bis(diphenylphosphino)-α-phenylalkane Complexes in Catalytic and Structural Studies
Brown, John M.,Murrer, Barry A.
, p. 489 - 498 (2007/10/02)
(R)-1,2-Bis(diphenylphosphino)phenylethane has been synthesised in good overall yield from (S)-mandelic acid ; its cationic rhodium(I) solvated complex has been shown to be effective in catalytic asymmetric hydrogenation with optical yields of up to 88percent having been observed.The n.m.r. spectra of complexes of this phosphine are discussed.Racemic (R*,R*)-1,3-bis(diphenylphosphino)-1,3-diphenylpropane and (R*,R*)-1,4-bis(diphenylphosphino)-1,4-diphenylbutane have been prepared.These form a range of rhodium complexes with dehydroamino-acids whose structures may be assigned on the basis of characteristic n.m.r.P-Rh and P-P coupling constants.
