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36.10.1.1.3 Method 3: Epoxide Ring Opening with Nitrogen Nucleophiles

DOI: 10.1055/sos-SD-036-00701

Bingham, M. J.; Greaney, M. F.Science of Synthesis, (200836983.

The β-amino alcohol moiety is a popular target for synthetic methods because of its presence in a large number of biologically relevant natural and synthetic molecules.[‌75‌] Cleavage of an epoxide ring with a nitrogen nucleophile represents a key synthetic strategy for the preparation of this class of compounds. The principles underlying the regio- and stereoselectivity observed in these reactions mirror those described previously for epoxide ring opening with oxygen nucleophiles (see Section 36.10.1.1.1). For the synthesis of products with primary amine functionality, an ammonia surrogate is often used. Treatment with sodium azide or trimethylsilyl azide, followed by reduction, is the most commonly used strategy, but consideration of the potential hazards associated with the use of azides has led to the development of a number of alternative ammonia surrogates, including N-(tert-butoxycarbonyl)-2-nitrobenzenesulfonamide,[‌76‌] tert-butyl or benzyl carbamates,[‌77‌] phthalimide,[‌78‌,‌79‌] and trifluoroacetamide.[‌80‌] Hydrazine,[‌81‌] hydrazides,[‌82‌] and nitrite[‌83‌‌85‌] are also suitable nitrogen nucleophiles for the ring opening of epoxides.

Mee eeeee- eee eeeeeeeeeeeeeee eeeeeeee ee eeeeeeee eeeeeeee ee eee eeeeee ee eee eeeeeee eeeeeeee eeeeeeee, eee eeeee eeee eeeeeeeee ee eeeeee β-eeeee eeeeeeee eeee eee ee eee eeeee eeeeeeeeeeee ee eeeeeeeeeeeeeeee eeee eeeeeeee. Me eee eeee ee eeeeeeee eeeeeeee, eee eeeeeeeeeeeeee ee eeee eeeeeee ee eeee eeeeeeeeee: eee eeeeeeee eeeeeeeeeee eeeeeee eeeeeee eee eeeee-eeeeeeee eeeeee ee eee eeeeeee. Meeeeee, eeee eeeeeeeeeee eee ee eeeeeeee ee e eeeeeeeeeee eeeeeee ee eeeeeeeeeee eee eeeeeeeeee eeeeeeee eeeeee ee eeeeee ee eeeeeee, ee ee eee eeee ee eeeeeeeeeeeee (eeeeeee eeeee, 88), eeeee, ee eeeeeeee eeee eeeeee eeeee ee eee eeeeeeee ee eeeeee(MMM) eeeeeeee, eeeee 88 eee 88 ee e 8:8 eeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meee Meeeeee ee Meeeeeee Meeeeeee eeee Meeeeeee Meeeeeeeeeee[‌88‌,‌88‌,‌88‌,‌88‌‌88‌]

Meeeeeeeeee 88

Meeeeeee ­Meeeeeee Meeeeeeeee Meeeeee(e) Meeee (%) Mee
MeMe88M8M (8.8 eeeee), MeM8 (8.8 eeeee), MeMM/M8M (8:8), eeeeee, 8e 88 [‌88‌]
e-MeMM8 (8 eeeee), MeMM, eeeeee, 8e 88 [‌88‌]
MeMM8 (8 eeeee), MeMe88M8M (8 eeeee), MMMM (8.8 eeeee), Me8M/M8M (8:8) 88 [‌88‌]
M8M8M8M, 88°M 88°M, 8e 88 [‌88‌]
M8MMMMM8 (8 eeeee), MMMMM (8.8 eeeee), M8MM8 (8.8 eeeee), 8,8-eeeeeee, 88°M 88 [‌88‌]
eeeeee eeeeeeee (8 eeeee), Me(MMe)8 (8.8 eeeee), MeMM, 88°M, 8e 88 [‌88‌]
MeMM8 (8 eeeee), Me(MMe)8 (8.88 eeeee), eeee, ee 88 [‌88‌]
eeeeeeeeee (8.8 eeeee), M8M, ee, 88e 88 [‌88‌]
MeMM8 (8.8 eeeee), M8M, ee, 88e 88 [‌88‌]

Mee MM8 eeee eeeeeee ee 8,8-eeeeeeeeeeeee eeeeeeee, eee eeeeeeeeeeeeeeee eeeeeeeeeeee eee eeee-eeeeee ee eee eeeeeeeeeee eeeee eeee eee-eeeeeeee eeee eee eeeeeeeeeeeee eee-eeeee eeeeeee eeeeeeee, eeeeeee eee eeeee-eeeeeeee eeee eeee-eeeee eeeeeeee. Meeeeee, eeeeeeee eee eeeeeeeeeeeeee eeeeeee ee eeeeeeeeeee, eee eeeeeeeee ee eeeeeeeee eee eeeeeee eeeeeee eeee eeeee eeeeeeeee eeeeeee ee ee eeeeeeeeeee eee eeeeeeeeeeeeee ee eee eeeeeee eeee eeeeeee. M eeeeeeeeeeeeeee eeeeeeee ee eeeeeeeeeee eeeeeeeeeeeeee eeeeeeee eeeeeeeeeeeeee eeeeeeee ee eee eeeeeeee eeeeeeeeeee, e eeeeeeee eeee ee eeeee eeee eeee eeeeeeeee eeeeeeeeeeee.[‌88‌] Mee eeeeeeeeeeeeee ee eeeeeeeeeeee eeeeee eee eeee ee eeeeeeeeee ee eee eeee ee 8,8-eeeee eeeeeeee (e.e., 88) eeeee eeeeeeee(MM) eeeeeeeeeeee ee eeeeeeeee eeeeee ee eeee γ-eeeee eee γ-eeeee eeeeeeee[‌88‌] ee β-eeeee eeeeeeee (e.e., 88),[‌88‌] eeeeeeeeeeee: ee eeee eeeee, eee eeeeeeeeeee eee ee eeeeeeeee ee eeeee ee e eeeeeee eeeee. α,β-Meeeeeeeeee eeeeee eeeeeee eee-eee eeeeeee eeeeeeeee eee eeee-eeeeeee eeee eeeeeeeeeeeeee eeeee ee eeee eeee-β-eeeee α-eeeeeee eeeeee eeee eeeeeeeee eeeee- eee eeeeeeeeeeeeeeeeee (eee Meeeee 88).[‌88‌] Meeeee eeeeeee ee eee eeeeeee eeeeeeeeeee eee eeee eeeeee eeeeeeeee eeeeeeeeeeee eeee eeee eeeee eeeeeeeeeeee eeee ee eeeeeeeeeeeeee eeeee, eeeeeeee eeeee eeeeeeeeee eee eeeee eeeeeeeee ee eeeeeee (Meeeee 88).[‌88‌] Meeeee 88 eeeee eeeeeeeeeeeeee eeeeeeee ee eeeeeeeeeeee eeee eeeeeee ee eeeeeeeeeeeeee eeeeeeee (e.e., eeeeeeeee ee eeeee 88).

Meeeee 88 Meee Meeeeee ee 8,8-Meeeeeeeeeeee Meeeeeee eeee Meeeeeee Meeeeeeeeeee[‌88‌,‌88‌,‌88‌,‌88‌‌88‌]

Meeeeeeeeee 88

Meeeeeee Meeeeeee Meeeeeeeee Meeeeee Meeee (%) Mee
Me8MM (eeeeee), Me(MeMe)8 (8.8 eeeee), ee, 8e 88e [‌88‌]
MeM8 (8 eeeee), M(MMe)8 (8.8 eeeee), MMM, 88°M 88e [‌88‌]
MeM, MMM, 888°M 88 [‌88‌]
MeM8 (8 eeeee), MM8Me (8 eeeee), MeMM/M8M (8:8), 88°M, 8e 88 [‌88‌]
8. MeMM (8 eeeee), MM8MMe8 (8 eeeee), MM8Me8, 8°M ee ee, 88e
8. eee. ee MeMMM8, 88e
88e [‌88‌]
88% ee MeMM8, MeMM, 888°M, eeeeeeee eeeeeee, 8e 88 [‌88‌]
MeMeM8 (8.8 eeeee), MeM8 (8 eeeee), MeMM, 88°M, 88e 88 [‌88‌]

e 8:88 eeeeeee ee 8-(eeeeeeeeeeeee)-8-eeeeeee eee 8-(eeeeeeeeeeeee)-8-eeeeeee eeeeeeeeeeee.

e 88:8 eeeeeee ee 8-eeeee-8-eeeeeee eee 8-eeeee-8-eeeeeee eeeeeeeeeeee.

e Meeeeeeeeeeeeee eeeeeee ee eeee, eeeeee ee eeeeeeeeeeeeeee eeeeeee (eeeeeeee eeeeeeeeeeeee eeeee).

Meeeee 88 Meee Meeeeee ee Meeeeeeeeeeeee Meeeeeee eeee Meeeeeee Meeeeeeeeeee[‌88‌‌888‌]

Meeeeeeeeee 88

Meeeeeee Meeeeeee Meeeeeeeee Meeeeee(e) Meeee (%) Mee
M8M=MMMM8MM8 (eeeeee), ­MeMeM8 (8 eeeee), 888°M, ­eeeeeeee eeee, 88e 88e [‌88‌]
MeM8 (8.8 eeeee), MeMM8 (8 eeeee), MeMM, eeeeee, 88e 88e [‌88‌]
MeM8, MM8Me, MMM/eeeeeeee eeeeee, 888°M, 88e 88 [‌888‌]
8. MeM8 (8.8 eeeee), Me(MM8)8 (8 eeeee), M8M (eM 8.88.8), 88°M, 8.8e
8. MeMM8 (8 eeeee), 8°M, 88eee
88 [‌888‌]
eeeeeeeeeee (8 eeeee), M8M, 888°M, 88e 88e,e [‌888‌]
8. MeM8 (8.8 eeeee), Me(MM8)8 (8 eeeee), M8M (eM 8.88.8), 88°M, 8.8e
8. MeMM8 (8 eeeee), 8°M, 88eee
88 [‌888‌]
88% ee MM8MM, eeeeeeeee (88M), 8eee 88e [‌888‌]

e Meeeeeeeeeeeeee eeeeeee ee eeee, eeeeee ee eeeeeeeeeeeeeee eeeeeee (eeeeeeee eeeeeeeeeeeee eeeee).

e Me 88% eeeee ee eee-eeeeeeee eeeee ee eeeeeeeee ee eeee eeeeeee eeeeeeeeee.

Meeeeeee eeeeeeee,[‌88‌,‌888‌] eeee-eeeeeeee,[‌888‌‌888‌] eee eeeee-eeeeeeee eeeeeeee[‌888‌] eee eeeeeee e eeeeeeeeeeeeee eee eeeeeeeeeeeeeeee eeee eeeeeee (eeeeeee eeeeeeeeee ee eeeeeeeeeeeeeeee), eeeee eeeeee eeeeeeeee eeee ee 88 (Meeeee 88), ee eeee eeeeeeeeeee ee eeeeee β-eeeee eeeeeeee (e.e., 88), eee-β-eeeee eeeeeeee, eee eeee-β-eeeee eeeeeeee, eeeeeeeeeeee. Me eee eeeeeee eeeeeeeeeee, eee eeeeeee eeeeeee ee eeee ee e eeeeeee eeeeee, eeeee ee eee eeeeeeee eeeeeeeeeee, ee eeeee eee e eeeeeee eeeeeeeeeee eeeee ee 888% eeeee ee eee eeeeeeeeeeee eeeeeeeee. Meeeeee eeeeeee eeeeeeeeee eeeeeeeeee ee eeeeeee eeeeeeee eee ee eeeeeeee eeeee e eeeeeee ee eeeeeeee eeeeeeeeeeee.[‌88‌]

Meeeee 88 Meeeeee Meeeeeeeee ee Meeeeee Meee Meeeeeee eeee Meeeeeee Meeeeeeeeeee[‌88‌,‌88‌,‌88‌,‌888‌,‌888‌]

Meeeeeeeeee 88

Meeeeeee Meeeeeee Meeeeeeeee Meeeeee ee (%) Meeee (%) Mee
MMMM8 (8 eeeee), (M,M)-88 (M=MeM8; 8eee%), 8°M ee ee 88 88 [‌888‌]
(M,M)-88 (M=MeMe; 8eee%), Me8MM8e (8 eeeee), MM8Me8, eee 88e 88 [‌888‌]
MeeMM8 (8 eeeee), (M,M)-88 (M=Me; 8eee%), 8-M8MM8M8MM8M (88eee%), e-MeMMe, ee, eee, 88e 88 88 [‌88‌]
(M,M)-88 (M=MeMMe; 8eee%), M8M (8.8 eeeee), MMM, 8°M ee ee, eeee MeeMMMee (8.8 eeeee), MMM, ee, 8e >88 88 [‌88‌]
Me8(eee)8MMMe8 (8eee%), MMMMM8 (8 eeeee), (M,M)-8, MM8Me8, 88 ºM 88 88 [‌88‌]
8. Me(MeMe)8/(M)-MMMMM/Me8Me=M (8:8:8) (8eee%), e-MeMMM/eeeeee (8.8 eeeee), MMM, 8-Å eeeeeeeee eeeeee, ee
8. MeM8 (8 eeeee), 88e
88 88 [‌88‌]

e Me8 = 8-MeMM8M8.

e Meeee (eeee/eee) >88:8.

e Me=8-eeeeeeeeeeeeeeeeeeee.

Meeeeeeeeeee Meeeeeeee

8-Meeee-8-eeeeeeeeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeee eeeee eee eeeeeee ee eeeeeee eee ee eeeeee eeeee. Meeeeee ee eeeee eeeeee eeee eeeee eeeeeeeee eee eeeeee eeeee eee eeeeeeeee eeeeeeeee eeee.

MMMMMMM: Meeeeeeeeeeee ee e eeeeeeeee eeeeeeeeee.

MeM8 (88ee, 8.8eeee) eee eeeee ee e eeeeeee ee eeeeeeeeeeeee (88; 888ee, 8eeee) eee MeMe88M8M (888ee, 8.8eeee) ee MeMM/M8M (8:8; 88eM), eee eee eeeeeee eee eeeeeee ee eeeeee eeeee eee eeeeeeee eee eeeeeeee (MMM, ~8e). Mee eeeeeee eee eeeeeeeee eeee MeMMe. Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M eee eeeee, eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee [eeeeee eee, MeMMe/eeeeee 8:88] ee eeee e eeeeeeeee eee; eeeee: 888ee (88%). 8-Meeee-8-eeeeeeeeeeeee (88) eee eeee eeeeeeee; eeeee: 88ee (88%).

(8M,8M)-8-Meeee-8-(eeeeeeeee)eeeeee-8,8-eeee (88); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeee eeeee eee eeeeeee ee eeeeeee eee ee eeeeee eeeee. Meeeeee ee eeeee eeeeee eeee eeeee eeeeeeeee eee eeeeee eeeee eee eeeeeeeee eeeeeeeee eeee.

M eeeeeee ee eee eeeee-eeeee eeeeeee 88 (M8=MM8MM; M8=MM8MMe; 8.88e, 88.8eeee), M(MMe)8 (8.8eM, 88.8eeee), eee MeM8 (8.8e, 88.8eeee) ee MMM (88eM) eee eeeeeee ee 88°M eee 8e eee eeee eeeeee ee 8°M. Mee. ee MeMMM8 eee eeeee eee eee eeeeeee eee eeeeeee eee 88eee. Mee eeeeeee eee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee MeMMe. Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeeeeeeeeeee eeee M8M, eee. ee MeMMM8, eee eeeee, eeee eeeee (MeMM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee ee eeee e 88:8 eeeeeee ee eeeeeeeeeeee; eeeee: 8.88e (88%).

(8M,8M)-(+)-8-Meeee-8-eeeeeee-8-eeeeeeeeeeeeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeee eeeee eee eeeeeee ee eeeeeee eee ee eeeeee eeeee. Meeeeee ee eeeee eeeeee eeee eeeee eeeeeeeee eee eeeeee eeeee eee eeeeeeeee eeeeeeeee eeee.

M eeeeeee ee (8M,8M)-8-eeeeee-8-eeeeeeeeeeeee-8-eeeeeeeeeee (>88.8% ee; 8eeee), MeM8 (8.88eeee), eee MeMM8 (8.88eeee) ee MeMM (88eM) eee eeeeeeee eee 88e. Mee eeeeeee eee eeeeeee eee eee eeeeeee eee eeeeeeee ee MeMMe. Meeee eeeeeeeeee eee eeeeeeeeeeeee, eee eeeeeee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeeeee eeeee 8:8) ee ee eeeeee ee eeee e eeeee eeeee; eeeee: 88%; [α]M88 888 (e 8.8, MeMM).

(M)-8-Meeee-8-(eeeeeeeeeeeeeee)eeeeeee (88); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: 8-Meeeeeeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee eeeeeeeee eeeeeeee eeee eee. Me ee ee eee, eeee, eee eeeeeeeeeee eeeee eeeeeeee eee e eeeeeeee eeeee eeeeeeeeee.

MMMMMMM: Meeeeeeeeeeeee eeeee eeeeee eeee eeeee ee eeee eee eeeeee eeeee eee eeeeeeeee eeeeeeeee eeee.

Me eeee-eeeee 88-eM eeeee eeeeeeee eeee e eeeeeee eee eee eeeeeee eeee eee eeeeeeee (M,M)-88 (M=MeM8; 88ee, 8.88eeee) eeee eeeeee, eeeeee eeee M8, eee eeeeee ee 8°M ee ee eee eeee. (±)-8-eeeeeeeeeeeee (888 μM, 8.8eeee) eee MMMM8 (888 μM, 8.8eeee) eeee eeeee eeeeeeeeeeee, eee eee eeeeeee eee eeeeeee ee 88°M eee 88e. Meeeeeee eeeeeee eee eeeeeee ee eeeeee eeeeeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeee (88°M/<8Meee) eeee e eeeeee eeeeeeeeee eeeee ee eeee e eeeeeeeee eee; eeeee: 8.888e (88%); 88% ee.

References


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