Science of Synthesis

Margaretha, P., Science of Synthesis, (2009) 40, 143.

Alkyl azides react with trivalent phosphines, most commonly triphenylphosphine, under very mild conditions to give iminophosphoranes (the Staudinger reaction). This reaction has been reviewed twice[‌83‌,‌84‌] and its importance in chemical biology has been highlighted.[‌85‌] The general mechanistic description implies the intermediacy of phosphazide ‌87‌, although an isomeric 1,1-triazene ‌88‌ would certainly represent a sound alternative. Hydrolysis of the iminophosphorane then affords the primary amine, with triphenylphosphine oxide as a (sometimes poorly separable) parallel product (‌Scheme 41‌).

‌Meeeee 88‌ Mee Meeeeeeeee Meeeeeee

M eeeee eeeeeee ee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee eeee eeeeee. Meeeeee M≡M eeeee[‌88‌,‌88‌] eee eeeeeee M=M eeeee[‌88‌] eee eeeeeeee ee eee eeeeeee. Me eeeeee eeeeeeeeee, e.e. eeeeeeeeeeeeeee, eeee eee eeeeeeeee eeeee eeeeee, eeeeeeeeee eeeeee eee eeeeeee ee eeee eeeeee ee eeeeeeeeee ee eeeee eeeeee, e.e. eeeeee, eee eee eeeeeeeeee, eeeeeee eeeeeeeee eee eeeeeeeeeeeeeeee.[‌88‌] Meee eeeee-eeeeeeeeeee eeeeeeeeeeeeee eeeeeeee eee eeeeeee eeeeeee ee eee eeeeeeeeeeeee eeeeee.[‌88‌] Meee eeeeeeee eeeeeeeee ee eeeeeeeeee eeeeeeeeee eeeeee ee eeeeeeeeeee ee ‌Meeeee 88‌ eee eee eeeeeeeee ee eeeeee ‌88‌ ee eeeeee ‌88‌.[‌88‌,‌88‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeee ee Meeeee eeee Meeeeeeeeeeeeeeeee–Meeee[‌88‌]

‌Meeeeeeeeee 88‌

Mee eeeeee eee eeee eeeeeee ee eeeeeee eeeeeee eeeeeeeee, e.e. ee eee eeeeeeeee ee M-eeeeeeeeeeeeeee,[‌88‌] ee 8-eee-eeeeeeeeee,[‌88‌] eee ee (–)-MMM8 eeeeee eeeee.[‌88‌] Meeeeee, eeeeeee eeeee-eeeeeeeeeeeeee eeeeeeeeeeeee ‌88‌ eeee eeee eeee eeeeeee ee eee eeeeeeeeeeeee eeeeee ‌88‌ ee eeee eeeeee, ee eeeeeeeeeee ee ‌Meeeee 88‌.[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee Meee-8-M-(ω-eeeeeeeeee)-β-eeeeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Me e 8 M eeee ee eeeee ‌88‌ ee MMM eee eeeee Me8M (8 eeeee), e eeeeeee eeee, eee M8M (8.8 eeeee). Mee eeee eee eeeeeee ee eeeee ee ee eee 88 e eee eee eeeeeee eee eeee eeeeeeeeee. Mee eeeeeee eee eeeeeee eeee e eeeeeee ee Me8M/eeeeee (8:8) eee eee Me8MM eee eeeeeee ee eeeeeeeeee eee eeeeeeeeee eeeeee eeee eee eeee eeeeeee eeeeeee. Meeeeeeeeeee eeeeeeee eee eeee eeeee; eeeee: 88–88%.

Meee-8-M-(ω-eeeeeeeeee)-β-eeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee ‌88‌ (8.88 eeee) ee e eeeeeee ee eeeeeee (88 eM) eee MeMM (8 eM) eee eeeee Me8M (88 ee, 8.88 eeee). Meeee 8 e, eeeee MM8 (8 eM) eee eeeee eee eeeeeeee eee eeeeeeeee eee 88 e. Meeee eeeeeee ee eee eeeeeeee eeeee eeeeeee eeeeeeee, eee eeeee eeeeeee eee eeeeeeeee ee M8M (88 eM) eee eeee eeeeee eeee MM8Me8 (8 × 88 eM). Mee eeeeeee eeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eeee eeeeeee ee e eeeeeee-eeeee eeeeee. Mee eeeeee eee eeeeeeee eeeeee eeee M8M (888 eM), 88% ee MeMM (888 eM), eee eeee 88% ee MeMM (888 eM). Mee eeeeeeeee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee eee eeee eeeee; eeeee: 88–88%.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) M 88e8, 888.