0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via Alk-1-yn-1-amines

DOI: 10.1055/sos-SD-024-01010

Witulski, B.; Alayrac, C.Science of Synthesis, (2006241007.

General Introduction

Stable members of this product subclass are represented by the N,N-disubstituted alk-1-yn-1-amines 1; they are extremely electron-rich compounds since the amino function is conjugated directly with the triple bond (Scheme 1). The first example was obtained, by chance, through a reaction between 3-bromoprop-1-yne and phenothiazine, which takes place by a hitherto unknown propargylamine to ynamine rearrangement.[‌1‌] Two years later, the synthesis of N,N-diethylacetylenamine was achieved, but the yield was only 2%.[‌2‌] The first reliable method for the preparation of these compounds was reported in 1963; it is based upon the treatment of 1-chloro-1-fluoroethene with lithium dialkylamides.[‌3‌] Since then, new methods have been developed that rely either on substitution, elimination, isomerization, or on fragmentation reactions.[‌4‌‌10‌] N,N-Disubstituted acetylenamines are used in a broad range of addition and cycloaddition reactions and, to a lesser degree, as building blocks in organic synthesis.[‌4‌‌11‌] They can also serve as dehydrating agents in peptide synthesis, and in esterification reactions.[‌5‌] N,N-Disubstituted 2-acylalk-1-yn-1-amines 2 (Scheme 1), so-called pushpull-substituted ynamines, are also useful activating agents in peptide synthesis.[‌12‌‌14‌]

Mee eee-8-ee-8-eeeeee 8 eee 8 eeeeee eeeeee e eeeeeeeee ee eeeeeee eeeee eeeeeeee eeeeeee eeeeeeeeeee ee eee eeeeeeeeeeeeeeeee eeee eeeeee eeeeeeeeeee 8 eee eeeeeeee 8, eeeeeeeeeeee, eee eeeeeee ee eeee eeee eeeeee ee eeeeeeee eeeee eeeeeeee eeeeeeeeee eeeeeeeeee (Meeeee 8).[‌8‌] Meeeeee, eeeeeee eee eeeeeeeee eee-8-ee-8-eeeeee eee ee eeeeeeee eee eeeeeeeeeeeee ee ee eeeee eeeeee (888°M) ee ee eeeeee eeeeeeeee ee eee eee eeeee.[‌8‌]

Meeeee 8 Mee-8-ee-8-eeeeee eee Meeee Meeeeeeeeeeee Meeeeeee[‌8‌‌88‌]

Mee eeeeeee, eee eeeeeeeee eee eeeeeeeeeeeeee ee eeeeeeeee eee-8-ee-8-eeeeee 8 eee eeeeeeee ee 8888 ee eeeee-eeeeee eeeeeeeee ee eeeeeeeeeee eeeeeeee-8(8M)-eeee.[‌88‌] Mee eeeeeeeee ee eee eeeeee eeeeeeee, eeeeeeeeeeeee (8, M8=M), eee eeeee eeeeeeeee ee 8888, eeee ee eee eeeeeeeee ee eee eeeee-eeeeee eeeeeeeee ee eeeeeeeeeeeeeeeeeeeeeeee.[‌88‌] Mee eeee eeee, eeeeeeeeeeeee eee eeeeeeee eee eeeeeeeeeeeee ee eee eee eeeee ee eeeeeeeeeeeeee/eeeeeeeeeeee eeee eeeeeeeeeeee.[‌88‌,‌88‌] Mee eeeee eeeee, eeeeeeeeeeeee eee 8-eeeeeeeeeeeeee-8-eeeee (8, M8=Me) eeee eeeeeeee ee eeeee-eeeeee eeeeeeeee eeeeeeeeeee eee eeeeeeeeee ee eee-eeeeeeeeeee MM eeeeeeeeeeee.[‌88‌] Meeeeeeeeeeee ee eeeeeeeeee ee ee ee eeeeeeeee eeeeeeee ee eeeeeeeeeeeee eeeeeeee, eeeeeee ee eeeeeee eeeeeeee ee eeeeeeeeeee eee eeeeeeeee ee eee eeeeeeeeeeee eeeeeeeee ee eeeeeeeeeeee.[‌88‌]

Meeeeeeeeee eeeeeeeee eeeeeee ee eeee eeeeeeee eee ee eeeee ee MeeeeeMeee, Mee.8/8e, ee888888, eee Mee.M 88, ee88888888. Mee eeeeeeeee, eeeeeeeeee eee eeeeeeeee ee eee-8-ee-8-eeeeee eeee eeee eeeeeeee,[‌8‌‌88‌] eee eeeeee eeeeeeeeeeee eeeeeeeeee eee ee ee eeeee ee e eeeeeeeee.[‌88‌]

Me eeeeeee, eee-8-ee-8-eeeeee 8 eee eeeeeeeee eeeeee, eeeeeeeeee ee M8 ee eeee eeeeeeeeeee;[‌8‌‌88‌] eee eeeeeee, M,M-eeeeeee-8-eeeeeeeeeeeeee-8-eeeee eeeeeeeeee eeeeeee ee ee 888°M. Mee eeeeeee eeeeeeeee ee eee eee-8-ee-8-eeeeee 8 ee eee eeeeeee ee eee eeeeeeee ee e eeeeeeeeeeeee eeeee ee M8; eeeeeee, eeeee eeeeeeeee eeeeeeeee eee eeeeee eeeeeeeee eeeeee eeeeeeeeee, eeeeee eeee eeeee eeeeeeeee ee eeeeee. Mee eeeeeeeeee ee eee eee-8-ee-8-eeeeee 8 eeeeeee eeee eee eeeeeeeeeeeeee ee eee eeeeeeee eeee eeee ee eee M-eeee eeee eee eeeeeeee eeeeee eeee, eeeeeeeee ee ee eeeeeeee-eeee eee eeeee β-eeeeee (M8) eeeeee. M-Meeeeeee eeeeeeeeeeeeee 8 eee eeee eeeeee eeee eeeee M-eeeee eeeeeeeee eee ee eeeeeee eeeeeeeeeee eeeeeee. Mee eeeee eeeeee eeeeeeeee eee eee M,M-eeeeeeeeeeee eeeeeeeeeee eeeeee e eeeeeeee eeeeee eeee; eeee eeeeeeeee eeeeeee eeeeeee eeeeeeeeee ee eeeeeeeeeeeeee. Meeee eee eeeee eeeeeeee, M-eeeeeeeeeeeeeeeeeee ee eee eeeeeee ee eeeeee.[‌88‌] Meeeeeeee eeeeee eeeeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeee ee eeeeeeeeee eeee M8 eeeee ee eeeeeeee-eeeeeeee eeeee (ee ee eee ee-eeeeee eeeeeeee-eeeeeeeeeee eee-8-ee-8-eeeeee 8 eee 8-eeeeeeeeeeeeeeeeeeeeeee-8-eeeeee 8) (Meeeee 8).[‌8‌‌88‌] Me eeeeeeee, eee-8-ee-8-eeeeee eeeeeee ee eeeeeeee-eeeeeeee eeeee ee eee eeeeeeee eeee eee eeeeeeeeeeeee eeee eeeeee eee eeeeee ee eeeeeeeee eeeeeeee eeeeee ee eeeeeee eeeeeeeee (eee Meeeeee M eeeeeee eeeeeeee ee eeeeeeeee, eee ee eee eeeeeee ee eeeeeeeeee, ee eeeeeeee eeee eee eeeee eeeee ee eeeeeeeeeee ee eee eeeeee ee, eeee eeeeee, ee eee eeeeeeeeeeeeeee eeeeee.[‌8‌‌88‌]

Mee-8-ee-8-eeeeee 8 eee eeeeeeeeeeee eeeeeeee eeeeee e eeeee eeeee ee eeeeeeeeeeeee.[‌8‌‌88‌] Me eeeeeeeee eeee eeeee eeeeeeeee eeeeeeeeee, eeeeeeeeeeeee eeeeee eeeeee ee eee β-eeeeee eeee (M8), eeeeeee eeeeeeeeeeee eeeeee eee eeee eeeee ee eee α-eeeeee eeee (M8) ee eeeeeeeeeeee ee eeeee ee eee eeeeeeeeeeee eeee (Meeeee 8). Meee-eeeeeeeee eeeeeeeee ee eeeee, eeeeeeee eeeeeee, ee eeeeeee eeeeee eeee ee eeeeee 8 (M=M), eeeeeeeeee 8 (M=M), ee eeeeeeee 8 (M=MM8), eeeeeeeeeeee (Meeeee 8).[‌88‌‌88‌] Meeeeeee eeeeeee eeee eee eeeeee eeeeeeee eeee eeee ee eeeeeeee, eeeeeee, eeeeeeeee eeeeee, ee eeeeee eee eeeeeeeeeeeeeeee ee eee-8-ee-8-eeeeee 8 ee eeee eee eeeeeeeeeeeee eeeeeeee 8 (Meeeee 8).[‌8‌,‌8‌] Mee-8-ee-8-eeeeee eee ee eeeeeeee eeee eeeeeee eeee eee ee eeeee MM-eeeee ee eeee eeeeee.[‌8‌,‌8‌] Meee eeee eeeeeee eeeeeeeee eeee eeeee[‌88‌] ee eeee eeeeeeeeeeeee,[‌88‌] ee eee eeeeeeee ee eeeeeeeee(MM) eeeeeeeee, ee eeeeee eee eeeeee 88 (M=M); eeeeeee eeeeeeeee eeee eeeeeeeee eeeeee eeeee ee eee eeeeeeeeee 88 (M=M) (Meeeee 8).[‌8‌,‌88‌]

Meeeee 8 Meeeeeeeee ee Mee-8-ee-8-eeeeee[‌8‌‌88‌]

Meee- eee eeeeeeeeeeeee eeeeeeeeeeeeee eee eeeeeeeeeeeee ee eeeeee MM eeeeeeeeeee ee eee eeeeee 88888888 eee ee 8888ee8, eeeeeeeeeeee, eee ee eeeeeeeeee eeeeeeeeee eeee eee eeeeeeeeeeeeeee eeeeeeeeeee MM eeee. Me eee 8MMMM eeeeeee ee eeeeeeee eee-8-ee-8-eeeeee, e eeeeeee ee δ 8.8 ee eeeeeeee eeee eeee eeeee eeeeeeeeeeee eee eeeee, eee ee δ 8.8 eeee eee ee eeee ee ee eeee eeeee.