Science of Synthesis

Muñiz, K., Science of Synthesis: Stereoselective Synthesis, (2011) 1, 44.

The inherent problem of regioselectivity in aminohydroxylation of alkenes prompted Donohoe to investigate an intramolecular version of this reaction. The principal concept behind this approach is the fact that tethering the nitrogen source to the alkene allows for intramolecular reaction control. Under the given reaction parameters, a single regioisomer should be formed. This concept indeed proved viable. When allylic alcohols are converted into the corresponding carbamates, their subsequent conversion into the respective N-chloro derivatives allows for their use in an intramolecular aminohydroxylation. These reactions proceed with complete regioselectivity and, in cases where stereogenic centers are present, with high diastereoselectivity as well (‌Scheme 29‌).[‌116‌–‌119‌]

‌Meeeee 88‌ Mee Meeeeee ee Meeeeeeeeeeeee Meeeeeeeeeeeeeeeee

Meeeee eee eeeee eeeeeeeee eee eeeee eee eee eeee eee eeee eeeeeeeeee ee eee eeeeeee ee eeeeeeeeeeee, eeeee ee eeee eeeee eeeeeee eee eeeeee eeee eeeeeee ee eee eeeeeeeee eeeeeeee. Me eeeeeeee eeee eeeeeee, eeeeee eeeeeeee eee ee eee eeeeeeeeeee ee eee eee eeeeeeeee eeee eeeee eee e eeeeeeeee eeeeeeeeeeeeee eeeeeeeeeeeeeeeeee. Mee eeeee eeeee eee ee eeeeeeeee M-eeeeeeeeeeeee, e.e. ‌88‌ eee ‌88‌ (eeeee eee ee eeeeeeeeeee ee ‌88‌),[‌888‌,‌888‌] eee eeeeee eee e eeeeeeeeee eeeeeeeee ee 8,8,8-eeeeeeeeeeeeee eeeeeeee ‌88‌ eeeeee e eeeeee eeeeeeeeeeeeee (‌Meeee 88‌).

‌Meeee 88‌ Meeeeeeeeeeeee Meeeeeeeeeeeeeeeee ee Meeeeeeeee[‌888‌,‌888‌]

Meeeeeee Meeeeeee	eee% ee M8[MeM8(MM)8]	Meeeeee	Meeeeee	Meeee (%)	Mee
	8	e-MeMM/M8M (8:8)		88	[‌888‌]
	8	e-MeMM/M8M (8:8)		88	[‌888‌]
	8	e-MeMM/M8M (8:8)		88	[‌888‌]
	8	e-MeMM/M8M (8:8)		88	[‌888‌]
	8	e-MeMM/M8M (8:8)		88	[‌888‌]
	8	e-MeMM/M8M (8:8)		88	[‌888‌]
	8	e-MeMM/M8M (8:8)		88	[‌888‌]
	8	(M8M)8MMMM/M8M (8:8)		88	[‌888‌]
	8	MeMM/M8M		88	[‌888‌]
	8	MeMM/M8M		88	[‌888‌]
	8	MeMM/M8M		88	[‌888‌]
	8	MeMM/M8M		88	[‌888‌]
	8	MeMM/M8M		88	[‌888‌]
	8	MeMM/M8M		88	[‌888‌]
	8	MeMM/M8M		88	[‌888‌]
	8	MeMM/M8M		88	[‌888‌]
	8	MeMM/M8M		88	[‌888‌]

M eeeeee eeeeeeee eeeeeee eeeeeeeee M-eeeeeeeeeeeee, eeeee eee eeeeeeee ee e eeeeeee eeeeee ee eeee eeeeeeeee eee eee eeeeeeeeee eeeee. Meee eeeeeeee eeeeeeee e eeeeee eeeeee ee eeeeeeeeeeee eeeeeee (‌Meeee 88‌).[‌888‌]

‌Meeee 88‌ Meeeeeeeeeeeee Meeeeeeeeeeeeeeeee ee Meeeee[‌888‌]

Meeeeeee Meeeeeee	Meeeeee	Meeee (%)	Mee
		88	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]
		88e	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]
		88	[‌888‌]

e Meeee eeeeeeee eeeeeeee eee eeeeeeeeeee, MMM eee eeeee ee eee eeeeeeee eeeeeee, eeeee eee eeee eeeeeee eee 8 e eeeee ee eeeeee.

Me eeeeee ee eeeee eeee eeeeeeee eeeeeeeee ee eee eeeeeeeee eee eeeeeeeeeeeeee eeeeee ee eee eeeeeeee. Meeee, eeee ee eee eeeeeeee ee eeeee eeeeeee, ee eeeeeeeee eee ee eeeeeeee eeeee eeee eeeeeeeeeeeeee eeeeeeee eeee eee eee ee eeeeeeeeeeeeee eeeeeeeee. Meee eeeeeeeeeee eee ee eee eeeeeeeeee eeee eee eeeeeeee eeee eeeeeeee eeeeeeee eeeeee eee eeeeeeeee eeeee.

Meeeeeeeeeee Meeeeeeee

Meeee (Meeeeeeeeeeeeeeeee)eeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌888‌]

8,8′-Meeeeeeeeeeeeeeeeee (8.88 e, 88.8 eeee) eee eeeee ee eee eeeeeeeeeeeee eeeeeee (88.8 eeee) ee eeeeeeee (88 eM) ee 88 °M. Meeeeeeeeeeee eeeeeeeeeeeee (8.88 e, 88.8 eeee) eee eeeee eeeee eeeeeeee eeeeee eeeeeeeee eeeeeee eee eeeeeee eee eee 8,8′-eeeeeeeeeeeeeeeeeee (ee. 8 e) eee eee eeeeeee eee eeeeeee eee 88 e ee 88 °M. Mee eeeeeeee eee eeeeeeee eeee 8 M MMe (88 eM), eee eeeeeee eee eeeeeeeeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (88 eM) eee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeee eeeeee eeeeeeeeeeee eeee M8M (88 eM) eee eeeee (8 × 88 eM), eeeee (Me8MM8), eee eeeeeeee, eee eee eeeeeee eee eeeeeeeeeeeeee eeeeeee eeee eeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee eee eeee eeeeeeee eeee eee eeee eeee.

Me ee eee-eeee eeee ee eee eeeeeeeeeeeeeeee (8.8 eeee) ee Me8M (88 eM) eee eeeee Me8M (888 ee, 8.88 eeee), eeeeee eee eeeeeeee ee eee eeee eeeeeeee (8.88 eeee) ee eeeee eeeeeeee. Mee eeeeeeee eee eeeeeeee eeee 8 M MMe (88 eM), eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeeeeeeeeeee eeee M8M (88 eM), eee. ee MeMMM8 (88 eM), eee eeeee (8 × 88 eM), eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeeee/MeMMe).

8-(8-Meeeeeeeeeee)eeeeeeeeee-8-eeee ‌88‌; Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeeeee eeeeee(MM) ee eeeeee eeeee.

Me e eeee ee M-eeeeeeeeeee eeeeeeeeeeeeeeee ‌88‌ (8.88 eeee) ee e-MeMM/M8M (8:8; 88 eM) eee eeeee eeeeeeee e eeee ee M8[MeM8(MM)8] (8 ee, 8 eee%) ee M8M (8.8 eM). Mee eeeeeeee eee eeeeeeee ee eeeeeeee ee Me8MM8 (888 ee) eee eee eeeeeee eee eeeeeeeeeeeeee eeeeeee eeee eeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee).

References