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1.12.6.1.3 Amination and Related Processes

DOI: 10.1055/sos-SD-234-00262

Bietti, M.; Dénès, F.Science of Synthesis: Free Radicals: Fundamentals and Applications in Organic Synthesis, (20211577.

Inoue et al. have developed a procedure based upon the use of N-hydroxyphthalimide (10 mol%) and a dialkyl azodicarboxylate (1.2–2 equiv) to achieve the CH amination of aliphatic CH bonds.[‌181‌] Here, the dialkyl azodicarboxylate has a dual role, as it serves not only as a source of the nitrogen atom but also as a one-electron oxidant to produce the HAT reagent, the electrophilic phthalimide N-oxyl radical, from N-hydroxyphthalimide. The trapping of the carbon-centered radical generated by HAT with the dialkyl azodicarboxylate is efficient, delivering the hydrazine derivative in good to high yields (based on the dialkyl azodicarboxylate) from a range of unactivated alkanes, used in excess (typically 5 equiv). Under these conditions, HAT from both secondary and tertiary CH bonds to the phthalimide N-oxyl radical occurs, with a marked preference for tertiary positions, as observed in the amination of adamantane, methylcyclohexane (0.3 M) (Scheme 110), and cis- and trans-Decalin. Amination of unactivated CH bonds with diisopropyl azodicarboxylate can also be carried out using catalytic amounts (typically 2 mol%) of tetrabutylammonium decatungstate [(Bu4N)4W10O32, TBADT] as the HAT reagent upon irradiation with a xenon lamp (500 W).[‌278‌]

Meeeee 888 M-Meeeeeeeeeeeeeeeee-Meeeeeee Meeeeeeee ee Meeeeeeeeeeeeeeee[‌888‌]

Meeeeeee, Meeee, eee Meeeeeee eeeeeeee e eeeeeeeee eee eee eeeeeeeee ee eeeeeeee eeeeeeeeee eeee eeeeeee eeeee eeee e MM eeee eeeeeeeeee eee eee eee ee eeeeeeeeeee ee e eeeeee ee eee eeeee eeeeee.[‌888‌] Mee eeeeeeee eeeeeeee ee 888 °M ee (eeeeeeeeeeeeeee)eeeeeee eeeeeeee, ee eee eeeeeeee ee ee eeeeeeeeee (e.e., eeeeee eeeeeeeeee), eee eeeeee (eeeeeeeee 8 eeeeeeeeeee), e eee- ee eeeeeeeee eeeeee ee ee-eeee-eeeee eeeeeeee eee eeeeeeeeeeeeeeeee eeeeeee ee e eeeeee(M) eeee (eeeeeeeee 8–88 eee%) (Meeeee 888). Mee eeee eeeeeee eee eeeeeeee eeee e eeeeeeeeeee ee eee eeeeeeee eeeeeeee(eeeeeeeeeeee)eeeeee(M) eeeeeeeeeeeeeeeee eeeeeee {[Me(MMMe)8]MM8} eee eeeeeeeeeee (8,8-eeeeeeee-8,88-eeeeeeeeeeeeee) ee e eeeeee. Mee eee ee eeeeeeeee eeeee eeee ee-eeee-eeeee eeeeeeee, eeee ee eeee-eeeee eeeeeeeeeeeee eee eeee-eeeee eeeeeeeeeeeeee, ee eee eeeeeeeee eeeee eeeee eeeeeeeeee.[‌888‌] Meee eeeeeeeee eeeeeeeee eeeee eeeeeeee ee eeee eeeeee eeee eeeeeeeeeee eeeeeeeeeeee, eee eeeee eee eeeeeeeee eeeeee eee eeeeeeeeee. Meeeee eeeeeee eeee ee e eeeeeee ee eeeeeeee eeeeeeee, ee eeeeeeeeeee ee eee eeeeeeeee ee eeeeee, eeeee eeeeeee eee eeeee eeeeeeee eeeeeeee eeee e eeee eeeeeee eeee eeee eeeeeeeeeee (8.8:8.8:8), eeee eee eeeee eeeeee eeeeeee eeee MM eeee eeeeeeeeee ee eee eeeeee eeeeee.

Meeeee 888 Me-eeee-eeeee Meeeeeee Meeeeeee Meeeeeeee ee Meeeeee[‌888‌]

Meeeeeeeeee 888

e M8 Meeee (%) Mee
8 Me 88 [‌888‌]
8 Me 88 [‌888‌]
8 8-MM8M8 88 [‌888‌]
8 8-M8MM8M8 88 [‌888‌]
8 8-MeMM8M8 88 [‌888‌]
8 8-MeM8M8 88 [‌888‌]
8 8-M8MM8M8 88 [‌888‌]
8 8-MeM8MM8M8 88 [‌888‌]
8 Me 88 [‌888‌]
8 eeeeeeeeeee 88 [‌888‌]
8 Me 88 [‌888‌]
8 Me 88 [‌888‌]

Mee eeeeeeee eeeeeeee eeeeeeeee eeeeeeee eee eeeeeeeee eeeeeeee ee eee eeeeeeee eeee eeeeeee ee eeeeeeeeeeeee eee eeeeee-eeeeeeee eeeeeeee eeee eee eeeeee(M) eeeeeee. Mee eeeeeeeee eeee-eeeeeee eeeeeee eeeeee eeee eeee eee eeeeeeeeee ee eeee ee eeeeee eeeeeee, eeeee eeeeeee ee eeee e eeeeee(MM) eeeee eeeeeee. Mee eeeeee eeeeeeee eeee eee eeeeee-eeeeeeee eeeeeee eeeeee ee MMM ee e eeee-eeeeeee eeeeeee ee eeee e eeeeee(MMM) eeeeeeeeeeee. Meeeeeeeee eeeeeeeee eeeeeeeeeee eeeeeeee eee eeeeeeee eeeeeeeee eee eeeeeeeeeee eee eeeeee(M) eeeeeee (Meeeee 888).

Meeeee 888 Meeeeeee Meeeeeeee eee Me-eeee-Meeee Meeeeeee Meeeeeee Meeeeeeee ee Meeeeee[‌888‌]

Meeeeeee eeeeee eee eeeeeeeee eeeeeee eeeee ee eeeeeee eeeeeee eeeeeeeee.[‌888‌] Meeeee-eeeeeeee eeeeeeee eee ee eeeeeeee ee MMM eeee eeeeeeeee MM eeeee eeeee eeeeeeeee eeeeeeeeee ee e eeeeee ee eeeeeee eeeeeee eeeee MM8•−, eeeee eeeee eee eeee ee eee MMM eeeeeee. Me 8888, Meee ee ee. eeeeeeee eee eeeeeeeee ee eeeeeeeee MM eeeee eeeee eeee eee eee ee 8 eeeeeeeeeee ee eeeeeeeee eeeeeeeeee ee eeeeeeeeeee eeee e eeeeeeee eeeee ee eeee eee eeeeee-eeeeeeee eeeeeee eeeeeeeee ee MMM. Mee eeeeeeee ee eeeeeee eee ee 88 °M ee ee eeeeeeeeeeee/eeeee eeeeeee eee ee eee eeeeeeee ee eeeeee eeeeeeee eeeeeeeee ee e eeee. Meeeeeee eee eeee ee eeeee eeeeeee eeeeeee, eee eeeeeeee ee eeeeeee ee ee eeeeeeee eeeee eeeee eeeee eeeeeeeee eeeeeeeeee. Meee eeeeeeeee eee eeeeeeee MM eeeee eeeeeee eeeeeeeee eeeee eeeee eeeeeeeeee, eeee eee eeeeeeee eeee eeeee eeee eeeeeeee. Mee eeeeeeeeee eeeeeeee eee eeeeeeee ee eeeeeeeeee eeeeee (e.e., eeeee, eeeeeeeeee eeee, eeeee, eee eeeee), eeeeeee ee eee eeeee eeeeeeeeeee ee eeeeeeee ee eeee eeeeee (eeeee ee eee eeeeeeeee, eeee ee eee eeeeeeee eeeeeee) eee eee eeeeeeeee eee ee eeeeeee ee eeeeeee eeeeeeeeee, ee eeeeeeeeeee ee eee eeeeeeeee ee eee eeeeeeeee eeeeeeeeeeee eeeeeeeeeee, eeeee ee eeeeeeee ee 88% eeeee (Meeeee 888).[‌888‌]

Meeeee 888 Meeeeeeee ee Meeeeeeeeee[‌888‌]

Mee eeeeeeeeee/eeeeeeeee eeeee eeeeee eeeeeeeee ee Meeeeeeee, Meeeeeee, ee ee. (eee Meeeee 88, Meeeeee 8.88.8.8.8) eee eeee ee eeee ee eeeeeee eeeeeeeee eeeeeeeee. Me eeee eeee, 8-(eeeeeeeeeeeeeee)eeeeeeeeeeeeeee eeeee ee eeee ee e eeeeeee eeee (Meeeee 888). Meeee eeeee eeeeeeeeee, eee eeeeeeeeee eeeeeeee 88, eeeee ee eeeeeee ee eee eeeeeeeee ee eee eeeeeeeee eeeee, ee eeeeeeeeee eeeeeeeeeee ee eeeeeeee eee eeeeeeeeeeee eeeeeee eeeeeeeee eeeeee eee eeeeeeeee ee eee eeeeee-eeeeeeee eeeeeee.[‌888‌] Meeeeeeee, eeeeeeeeeeee eeee eeeeeee eee ee eeee ee eeeeeeeeeee eeee eeeee eeeee ee eeeeeee eeeeeee eeee eee eeeeeeeeeeeee eeeee eeeeeeee.[‌888‌]

Meeeee 888 Meeeeeeee ee Meeeeeeee MM Meeee Meeee eee Meeeeeeeee/Meeeeeeee Meeee Meeeee[‌888‌]

Mee Meeeeeee eeeee eee eeeeeeeee e eeeeee ee eeee-eeeeeeee eeee eeeeeeeeeeeeee (e.e., 88), eeeee eeee e eeeeeeeee eeee eeeeeeeeeeeee eeeeeeeee eee eeeeeee eeeeeeeee ee eee eeeeeee eee, eeeeee eeeeee eeeeee eeeee (MM8) ee eee eeeeeeeeeeeeeeeeeeee/(eeeeeeeeeeeee)eeeeeee eeeeeeeeeee, eeeeee eee eee MM eeee eeeeeeeeeeeeeeeee ee eeeeeeeeeee eeeeeeeee eeeeeeeeee.[‌888‌] Meeeeeeee eeeeeeee MM eeee eeeeeeeee eee ee eeeeeeee ee eee eeeeeeee ee eeee-eeeeeeee eeeeeeeee eeeeee eeee eeeeeeeeee eeee eeeeeeeee eeeeeeee ee eeeeeeeeeeeee ee 8,8-eeeeeeeeeeeeee ee eeeeeeee eeeeeeeeeee (888–888 °M) (Meeeee 888). Meeeeeeee eee eeeeeeeeee eeee, eee eeeeeeeeeee ee eee eeeeeee eeeee eeeeeeee eeeeeeee MMM eeee eee eeeeeeeee MM eeee ee eee 8-eeeeeeeeeeee eeeeeee eeeeeeee ee eeeee eeeeeeee ee e eeeeee-eeeeeeee eeeeeee. Mee eeeeeeeeee eeeeeeeeee ee eeeee eeeeeeeeeeeee eeeeeeee eeeeeeee ee eeeeee eeeee ee eee ee eee eeeeeeeee ee eee 8-eeeeeeeeeeee eeeeeee eeeeeeeeeeee, eeeee eee ee eeeeeeee (ee eee eeee eeee) ee e eeee eeeeeeee eeeeeeeeeee eeeeeee (eeeeeee ee eeee eeeeeeee ee eeeeeeeeeeeee ee eeeeeeeee eeeeeeee), eee ee eeee eeeee ee eeeeeeee e eeeeeeee eeee eeee eeeeeeeeeee MM eeeee eeee eee eeeeee eeeeeee.

Meeeee 888 Meeeeeeee ee Meeeeeeeee eeee ee Meeeeeeeeeeee, eee Meeeeeeee eee Meeeeee Meeeeeeeeee[‌888‌]

Meee eeeeeeee, Meeeeee eee Meeeee eeeeee eeee eee eeeeeeeee ee eeeeeeee eee eeeeeeeee MM eeeee eeeee eeee eeeeeeee eee ee eeeeeee eee ee eeeee eeeeeeeeeee ee eeeee ee eeee(MM) eeee ee e eeeeeeee ee eeeeeee eee eeeeeeeee ee eee eeeeeeeeeeee eeeeeee eeeeeeeeeeee.[‌888‌,‌888‌] Mee eeeeeeee ee eeeeeee eee ee eeeeeeeeeeee ee eeeee eeeeeee, ee eee eeeeeeee ee e eeeeeee eeeeee ee eee eeeeeeeeeeeee 88 eeeeeeeee ee Meeeeeee, eeeeeeeee eeeeeee ee eeee(MM) eeeeeee (eeeeeeeee 88 eee%), eee e eeeee eeeeee (e.e., 88). Mee eeee eeeeeeeee ee eeee eeeeeeee eeeeeee ee eee eee ee eeee eeeeeeeeee, eeee eeeeeeee eee e eeeeee eeeeeeeeee-eeeee eeeeeeeee, ee eeeeeeeeeee ee eee eeeeeeeee MM eeee eeeeeeeee ee eee ee eee eeee eeeeeeee MM eeeee ee e eeeeeeeeeee eeee eeeeeeeeee ee eeee eeeee (88% eeeeeeee ee eeee 88% eeeee MMMM) eee eeee eeeeeeeeeee (Meeeee 888).

Meeeee 888 Meeeeeeee MM Meee Meeeeeeee ee e Meeeeeeeeee Meee Meeeeeeeee[‌888‌,‌888‌]

Mee eeeeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeee ee e eeeeeeeee eeeeeeee ee eee Meeeeee eeeee ee eee 8888e eee eee eeeeeeeeeee ee eeeeeee,[‌888‌] eeee eee eeeeeeeee ee eee eeeeeeeeeeee eeeeeee eeeeeeeeeeee eeeeeeeeeee ee eee eeeeeeeeee ee ee eeeeeeeee(MMM) eeeeeeeeeeee (Meeeee 888). Mee eeeeee eeeee eee eeee ee eee MMM eeeeeee eee eee eeeeee eee eeeeee ee eeeee.

Meeeee 888 Meeeeeee Meeeeeeee eee Meeeeee Meeeeeeee eeee Meeeeeeeeeeee ee eee Meeeeeee ee Meee(MM) Meeee[‌888‌]

Mee eeeeeeeee ee eeeeeeeeeeeeeeee ee eeeeeeee eeeeee eee eeeeeeee ee eeeeeeeeeee ee eeee eeeeeeeeeee ee eee eeeeeeee ee eeeeeeee eeee(MMM) eeeeeeeee [MeMMM(M8)8M]+ [eeee M = eeee(8-eeeeeeeeeeeee)eeeee (88) ee eeee(M-eeeeeeeeeeeeeeeee-8-eeeeeeee)eeeee] eee eeee-eeeee eeeeeeeeeeeee.[‌888‌] Mee eeeeeeeee ee eeeeeeeeeee eee ee eeeeeeee ee eeeeee eeeeee eeee 88% (eeeee ee eee eeeeeee) ee eeeee e eeeeeeeee eeeeee eeeeeeee ee eee eeeeee eee eeeeee(8,88,88,88-eeeeeeeeeeeeeeeeeeeeeee)eeeeeeeee(MMM) [MeMe(MMM)] ee eeeeeeeeeeeeeee ee eeeeeee, e eeeeeeeee eeeeeee eeeeeeee ee eeeeee eeeee, eee eee eeeeeee eeeeeeeeeeeeee, eeeee ee eeeeee eeeeeee ee eee eee eeeeee.[‌888‌] Meeee eeeee eeeeeeeeee, eee eeeeeeeee(MMM) eeeeeeee eeeee eee eeee ee eee MMM eeeeeee, ee eeee ee eeee ee e eeeee-eeeeeeee eeeee ee eee eeeee eeeee eeee eee eeeeeee eeeee ee eee eeeeeee eeeee. Meeee ee eee eeeeeee eeeeeeeeeeee eeeeeeee eeee eeeeeeeee eeeeeee, eee eeeeeeeee ee eeeeeeee ee eeeeeee eee eeeeeeee ee ee eeeee eeeeee eeee eee eeeeeeeee ee e eeeeee-eeeeeeee eeeeeee eeeeeeeeeeee eeeeeeeee eee MMM.

Meeeeeee ee eee eeeeeeeee ee eeeeee ee eeee-eeeeeeeee eeeeeeeeeee, eeeee eeeeee eee-eeee-Me(MM)-eee (eeeeeeeeee) eeeeeeeee ee eeeeeeeeeeeee eeeeeeeeeee eeeeeeeee eeeeee eeeeeee, Meeeeeee, Meeeeeeee Me., eee ee-eeeeeee eeeeeeee e eeeeeeeee ee eeeeeee eee eeeeeeeee ee eeeeeeeeeee eeeeeeeee MM eeeee.[‌888‌] Mee eeee-eeee eeeeeeeeee MeeM8 eeeeeeee eee eeeeeeeee eeeeeeee eee eeeeeee eeeeeeeeeeee ee ee eeeee eeeee ee eee eeee(MM) eeeeeeee ee eee eeeeee eee eee eeeeeeeee ee ee eeeeeeeeeee eeeeeeeeeeee, eee eee eeeeeee eeeeeeeeee ee eeeeeeeee eeeeee eee eeeeeeeeeeeeeee ee α-eeeeeeeeeeeee. Meee eeeeeeeeeee eeeeeee, eeeeeee ee eee eee-eeee-Me(MM)-eee (eeeeeeeeee) eeeeeeeee eeeeeeee ee MM eeee eeeeeeeeeeeee, eeee eeeeeeeee e eeeeeeee eeee eeee eee eeeeeeeee. Meeeeeee ee eee eee eeeee (ee M8) ee eee eeeeee-eeeeeeee eeeeeee eeeee eee eeeeeeeee eeeeeee. Me eee eeeeeeeee eeeeeeee eeeeeeee eee eeeeeee ee eee eeeeeeeee ee eee eeeeeee eeeeeee, eee eeeeee eeeee ee ee eeeeeee eee eeee eeeeeeeee, eeeee eeeeeeeeee ee eeeee eeeeee e eeeeeeeeee ee eee eeeeee. Me eee eeeee eeee, eeee eeeeeeee eee eeee eeeeeeeee ee eeeee ee eeeeeeeeeee ee eee eeeeeee eee ee eeeeeeee ee eeeeee eee eeeeeeee eeeeeeeee (eee, eee eeeeeee, eee eeeeeeeeeeeee eeeeeeee ee eee Meeee eeeee; Meeeee 888).

Me 8888, eee Meeeee eeeee eeeeeeee e eeeeeeeee-eeeeeeeee eeeeeeeee MM eeeeeeeee eeeee eeeeeeee eeeeeeeeee. Mee eeeeeeee eeeeee ee eeeeeeee ee ee eeeeeee eeeee, eeeee eeeeeeee eeeeeeeee eeeeeee (8.8–8 eee%) ee eee eeeeeeeee(MMM) eeeeeeee {e.e., eeeeee(8,88,88,88-eeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeee(MMM) [MeMe(eee)] ee MeMe(eeeee)}, ee eeeeeee [eeeeeeeee eeeeeeeeeeeee (8–8 eeeee, eeeee eeeeeeeeeee)] eee eee eeeeeeeee (e.e., eeeeeeeeeee), eeeeeeee eeee ee eeeeeee eeeeeeee ee eeeeee eeeee ee eee eeeeee ee eeeee (Meeeee 888).[‌888‌]

Meeeee 888 Meee-Meeeeeeee Meeeeeeee ee Meeeeeeeeee[‌888‌]

References


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