Assignment stereospecific

Although the emphasis in this chapter has been on tbe synthesis and mechanism of formation of simple enamines, brief mention will be made of the addition of amines to activated acetylenes to indicate the interest and activity in this area of substituted enamines. Since such additions tend to be stereospecific, inclusion in this section seems apropos. The addition of amines to acetylenes has been much studied 130), but the assigning of the stereochemistry about the newly formed double bond could not be done unequivocally until the techniques of NMR spectroscopy were well developed. In the research efforts described below, NMR spectroscopy was used to determine isomer content and to follow the progress of some of the reactions. 

An isomeric sugar, D-javose, is a constituent of two cardenolide glycosides (strophanthojavoside and antiarojavoside) found (42) in the seeds of Antiaris toxicaria Lesch. Degradative studies indicated (42) that javose had the structure 6-deoxy-2-0-methyl-D-allose (17) and this assignment was confirmed by two stereospecific syntheses. 

In view of the possible ambiguities which can attend conformational assignments based on vicinal coupling constants, it is fortunate that both long-range and geminal couplings each exhibit stereospecific dependences. 

Senn H, Werner B, Messerle BA, Weber C, Traber R, Wuthrich K. Stereospecific assignment of the methyl H NMR lines of valine and leucine... 

Giintert P, Braun W, Billeter W, Wiithrich K. Automated stereospecific 1H NMR assignments and their impact on the precision of protein structure determinations in solution. J Am Chem Soc 1989 111 3997-4004. 

Epoxidation of the 3,4-dihydrodiol with m-chloroperbenzoic acid afforded stereospecifically the corresponding anti diol epoxide (74). Peracid oxidation of the bay region 1,2-dihydrodiol gave a mixture of the anti and syn diol epoxide diastereomers. Assignment of the major isomer as syn was made through analysis of the NMR spectra of the acetates of the tetraols formed on hydrolysis of the individual diol epoxides (42). Peracid oxidation of the 10,11-dihydrodiol is reported to yield the corresponding anti diol epoxide (12). However, it is likely for steric reasons that the syn isomer is also formed. 

A novel intramolecular bis-silylation of propargylic disilanyl ethers followed by a Peterson-type syn elimination provides access to a variety of allenylsilanes (Table 9.36) [57]. The elimination is initiated by treatment of the presumed four-membered siloxane intermediate with BuLi. This intermediate could not be isolated, but spectral data were in accord with the assigned structure. The cycloaddition and elimination steps were shown to take place stereospecifically (Eq. 9.48). 

Independent proof of these assignments is obtained from chemical studies. In the g/Mco-derivative (54), the hydroxyl groups at C-2 and C-4 can be inverted stereospecifically via oxazolidine derivatives with the neighboring amino group, thus unequivocally proving the stereochemical relationships between C-2, C-3 and C-4 in compounds (54)— (56) 10). 

The lithium-(—)-sparteine complexes, derived from primary 2-alkenyl carbamates, are usually configurationally labile even at —78 °C. During the investigation of the (ii)-crotyl carbamate 301, the (—)-sparteine complex (5 )-302 crystallized in a dynamic thermodynamic resolution process (equation 76) and stereospecific substitutions could be performed with the slurry An incorrect assignment of the configuration of the lithium inter-... 

A longer-range coupling has been detected in 140, between the ringed hydrogen atoms, and the stereospecificity used to assign the conformation. (1988,117)... 

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