Science of Synthesis

Bräse, S.; Lesch, B.; Zimmermann, V., Science of Synthesis, (2010) 41, 560.

Azides can be prepared in excellent yields with complete inversion of configuration starting from enantiomerically pure secondary alcohols, by reacting with methanesulfonyl chloride, 4-(dimethylamino)pyridine, and an excess of sodium azide in dichloromethane at 0°C to room temperature.[‌77‌] As an example, the synthesis of (S)-8-azido-5,6,7,8-tetrahydroquinoline (‌60‌) is shown in ‌Scheme 27‌.

‌Meeeee 88‌ Meeeeeeeeee ee (M)-8-Meeee-8,8,8,8-eeeeeeeeeeeeeeeeeee[‌88‌]

M eeeeeee, eeeeeeeeeeeeeee eeeeeeeee ee α-eeeee eeeee ‌88‌ eeeeee eeee eeeeeeeeeeeeeeee eeee 8,8,8-eeeeeeeeeeeeee-8-eee ‌88‌. Meeee eeeeeeee eee eeeeeee eeeeeeeee eeee eeeeeeeeeeeeeee eeeeeee ‌88‌ eeee eeeeeeeeeeee eeeeeeee ee >88% ee eeeeeeeeee eeeeeeeee eeee 8,8,8-eeeeeeeeeeeeeeee (‌88‌, eeeeeeeeeeeeee) ee eee eeeeeeee ee (8eM)-8-eeeee-8,8-eeeeeeeeeeeeeeeeee-8M-eeeeeee[8,8-e][8,8,8]eeeeeeeeeee (‌88‌) (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeeeeeeeee Meeeeeeee ee 8-Meeee Meeee[‌88‌]

‌Meeeeeeeeee 88‌

M8	Meeee (%) ee ‌88‌ eeee ‌88‌	Mee
(MM8)8Me	88	[‌88‌]
(MM8)8Me	88	[‌88‌]
8-MeM8M8MM8	88	[‌88‌]
	88	[‌88‌]
Me	88	[‌88‌]
e-Me	88	[‌88‌]

Mee Meeeeeeee eeeeeeee eeeeeeee e eeeeee eeeeee ee eeeeeee eeeeee eeee eeeeeeee.[‌88‌–‌88‌] Meeeeee eee eeeeeeeee eeeeeeee (e.e., ‌88‌) eeeee eeee eeeeeeeee eeee, eeeeeeeeeeeeeeeeee, eee eeeeeeeeeee ee eeeeeee eeeeeeeeeeeeeeee ee eeee eee eeeeeeeeeeeee eeeeee (e.e., ‌88‌) (‌Meeee 8‌). Meeeeeeee eeeeeeee eee ee eeeeeeeeee eeeeeeee ee eeeeeeeeee eeeee eeee eeeee eeee eeeeeeee eeeeeeeee ee eee eeeeeeeeeeeee. Meee eeeeeeeee eeeee Meeeeeeee eeeeeeeeee eee eeee eeee eeeeeeeeeeee ee eee eeeeeeeee ee eeeeeee eeeeeeee eeee ee eee eeeeee eeeeeeee (–)-eeeeeeeeeeee M.[‌88‌]

Meeeeeee eeeeeeeeeeeeeee (MMMM) eee eeee ee eeee eeeeeee ee eee eeeeeeeee eeeeeeeee eeee.[‌88‌,‌88‌] Meeeeee eeeee eeeeee eee Meeeeeeee eeeeeeeee ee eeee(MM) eeeee.[‌88‌] Meeee eeeeee eee eeee ee eeeeeeee ee eee eeeeeeee ee eeeeeeee eeee e eeeeeee eeeeeee ee eeeeee eeeeeeeeeeee, eeeeeeeeeeeeeeeeee, eee eeeeee eeeee.[‌88‌] Meeeeee eeeeeeee eeeeeeeee ee Meeeeeeee eeeeeeeeee ee 8°M eeeeeee eee eeeeeeeeeeeee eeeeeee eeeeee,[‌88‌] eeeeeeee eee eeeeeeeeeeeeeeee eee ee eeeeeeee eee ee eee eeeeeee [8,8]-eeeeeeeeeee eeeeeeeeeeeeee ee eeeeeee eeeeee ee eeee eeeeeeeeeee.[‌88‌]

‌Meeee 8‌ Meeee Meeeee eeee Meeeeeee eee Meeeeeeee Meeeeeee[‌88‌,‌88‌,‌88‌,‌88‌–‌88‌]

Meeeeeee Meeeeeee	Meeeeeeeeee	Meeeeee	Meeee (%)	Mee
	MM8, Me8M, MMMM, eeeeeee, 88°M, 8 e		88	[‌88‌]
	MM8, Me8M, MMMM, eeeeeee, 88°M, 8 e		88	[‌88‌]
	MM8, Me8M, MMMM, MM8Me8/MMM, 8°M, 8 e		88	[‌88‌]
	8. MM8, Me8M, MMMM, eeeeeee, 8°M, 8 e 8. 8°M ee ee, eeeeeeeee		88	[‌88‌]
	8. MMMM, Me8M, MMMM, MMM, −88°M, 8 e 8. −88°M ee ee, eeeeeeeee		88	[‌88‌]
	8. MMMM, Me8M, MMMM, MMM, 8°M, 8 eee 8. 8°M ee ee, 88 e		88	[‌88‌]
	Me(M8)8•8ee, Me8M, MMMM, eeeeeee, 8°M, 88 e		88	[‌88‌]
	MeM8, MMe8, Me8M, MMM, ee, 88 eee		88	[‌88‌]

e MMMM = eMeM8MM=MMM8eMe; MMMM = (MeM)8M(M)M8.

Mee eeeeeeeeeeeee ee eee Meeeeeeee eeeeeeeeee (eeeeeeeeeee eeeeeeeeee ee eeeeeeeee eeeeee eee eeeeeeeee eeeee, eeeeeeeeeee-eeeeeee eeee eeeeeeee) eee ee eeeeeeee ee eee eeeeeeeeeee ee 8,8-eeeeeeeeeeee[8.8.8]eeeee-8-eee eee eeeeeeee eeeeeeeeeeeeeee (‌Meeee 8‌).[‌88‌] Meee eeeeee eeeee eeee eeee eeeeeeeee eeeeeeeeee eeee ee eeeeeeee eeeeeeee eee α-eeeeeeeeeeeeeeeee eeee eeeeee eee ee eee eeeeeeeeeeee eeeeeeee eee eeeee eeeeeeee. Mee eee ee eee eeeeeeee eeeee eeeeeee eee(8-eeeeeeeeeee) eeeeeeeeeeeeeee eeeeeeeee eee eeeee ee eeeeeeee eeeeeeeeee; eeeeeee, eeeeeeeeeeeee eee eeeee eee eeeeeeee eeeeee eee eeeeeee eeeeeeee eeee eeeeeeeeeeee.[‌88‌] Mee eeee eeeeeeee ee eee eeeeeeee eee ee eeeeee eeeeeee ee eeeeeee eeee eeeee.

‌Meeee 8‌ Meeeeeeeeee ee Meeee Meeeee eeee Meeeeee eee Meeeeeeee Meeeeeee Meeee Meeeeeee Meeeeeeeeeeeeee–8,8-Meeeeeeeeeee[8.8.8]eeeee-8-eee eee Meeeeeeee Meeeeeee[‌88‌,‌88‌]

Meeeeeee Meeeeeee	ee (%) ee Meeeeeee Meeeeeee	Me8	Meeeeeeeee	ee (%) ee Meeeeee	Meeeeee	Meeee (%)	Mee
	88.8	Me	eeeeeee, 88°M, 88 e	88.8		88	[‌88‌]
	>88	8-M8MM8M8	MMM, 88°M, 8 e	>88		88	[‌88‌]
	>88	8-M8MM8M8	MMM, 88°M, 8 e	88		88	[‌88‌]
	88.8	8-M8MM8M8	MMM, 88°M, 8 e	88		88	[‌88‌]
	88.8	8-M8MM8M8	eeeeeee, 88°M, 8 e	88		88	[‌88‌]
	88e	8-M8MM8M8	eeeeeee, 88°M, 8 e	88e		88	[‌88‌]
	–	8-M8MM8M8	MMM, 88°M, 8 e	–		88	[‌88‌]
MeMM	–	8-M8MM8M8	eeeeeee, 88°M, 88 e	–	MeM8	8	[‌88‌]

e Meeee ee ee eeeeee eeee ee.

Meeeeeeee ee eeeeeeee ee e eee-eeee eeeeeeeee–eeeeeeeee eeeeeeeeeeee eee eeeee eeeeeeeeeeeeeeeeeeee eee eeee eeeeeeeee.[‌88‌] Meeeeeee ‌88‌ eee eeeeeee eeee eeeeeeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeee eee e eeeeeeeee eeeeee ee 8-(eeeeeeeeeeeee)eeeeeeee eeeeee eeeee eeeeeeeeeeee ‌88‌. Meeeeeeee ee eeeee eeeeeeeeeeee ‌88‌ eeee eeeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee 8-eeeeeeeeeeee-8,8-eeeeeee (‌88‌) eeeeee eeeee eeeeee ‌88‌ (‌Meeeee 88‌). Mee eeeeeee eee eeee eeeeeeeeee ee eee Meeeeeeee eeeeeeee eee eeeeeeeeeeee eeeeeeeeeeee ee eee eeeeeeeee ee eeee-eeeee eeeeee. Meeeee eeee-eeeee eeeeeeee eee eeeeeeeee eeee eee eeeeeeeeeeeee eeeeee eeee-eeeee eeeeee eeee eeeeee eeeeeeee eeeeeeeee ee eeeeeeeeeeeee. Meee eeeeeeee eeeeeeee eeeeeeee, eee eeeeeeeeeeee eeeeeeee eee eeeeeeeeeeeee eeeee.

‌Meeeee 88‌ Meeee Meeeee eeee Meeeeeee eee Meeeeeeee Meeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Meeeeeeee (%) ee eeeeeee ee (ee ee eeeeeeee eeeeeeee ‌88‌)/(ee ee eeeeeee ‌88‌).

e Meee 8.888 eeeee ee MMMM8 eee eeee; eeeee eeeee ee MMMM8.

e (M)-Meeeeeeeee (88% ee) ee eeeeeeee eeeeeeee eee eeee.

e (M)-Meeeeeeeee (88% ee) ee eeeeeeee eeeeeeee eee eeee.

Meeeeeeeee eeeeeeeee ee eeeee-8-ee eeee eeeeeeee eeeeeeeeeeeeeee ee eee eeeeeeee ee e eeeeee eeeeeeeee eeeeeeeee eee eeee eeeeeeee, eeeeeeeee 8-eeeeeeeeeee ee 88% eeeee eee eeee 88% ee.[‌88‌]

Meeeeeeeeeee Meeeeeeee

(M)-8-Meeee-8,8,8,8-eeeeeeeeeeeeeeeeeee (‌88‌):[‌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: Mee eeeeeee ee eeeeeeeeeeeeeee eeee eeeeee eeeee eee eeeee eeeeee eeeeeeeee eeeeeeeeeeeeee.

Me e eeeeeee ee (M)-8,8,8,8-eeeeeeeeeeeeeeeeee-8-ee (88 ee, 8.88 eeee), MMMM (888 ee, 8.88 eeee), eee MeM8 (8.8 e, 88 eeee) ee MM8Me8 (8 eM) eee eeeee MeMe (888 ee, 8.88 eeee) ee 8°M. Mee eeeeeee eee eeeeeee ee ee eee 88 eee. MMMM (8 eM) eee eeeee eee eee eeeeeee eee eeeeeee eee ee eeeeeeeeee 8 e. Mee eeeeeeee eee eeeeeeee eeee M8M, eee eee eeeeeee eee eeeeeeeee eeee eeeeee/MeMMe (8:8). Mee eeeeeee eee eeeeee eeee M8M eee eeeee, eeeee (MeMM8), eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 88:88); eeeee: 88%; Me 8.88 (eeeeee/MeMMe 8:8); [α]M88 −88 (e 8.88, MMMe8); MM (eeee) ν̃eee: 8888 ee−8 (M8).

(M)-8-Meeee-8,8-eeeeeeeeeeeeeeee Meee (‌88‌, M8 = e-Me); 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.

Meeeeee ‌88‌ eee eeeeeeee ee eeeeeee: M eeeeeee ee (M)-eeeeeeee(eeeeeeeeee-8-ee)eeeeeeee (8.888 e, 8.88 eeee), eeeeeeeeeeee eeee (8.888 e, 8.88 eeee), eee eeeeeee (88 eM) eee eeeeee ee eeeeee eeee e Meee–Meeee eeeeeeeee eeeeeeeeee 8-Å eeeeeeeee eeeeee eeeee M8 eee 88 e. Mee eeee eee eeeeeeeeeeee ee 8 eee ee 8 eM, eeee eeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eeee eeeeeeee, eee eeeeeee (88 eM), eeeeeeee e 8.8 M eeee ee eee eeeeee eeeeeeee ‌88‌. 8,8,8-Meeeeeeee-8,8-eeeeeeeeeeeee-8-eee (‌88‌, M8 = e-Me; 8.88 e, 88.8 eeee) eee eeeee, e 8 M eeee ee eeeeeee eeeeeeeee 8,8,8-eeeeeeeeeeeeeeee (‌88‌) ee eeeeeee (88 eM, 88.8 eeee) eee eeeee eeeeeeee eeee 88 eee ee −88°M eeee eeeeeeee eeeeeeee, eee eeee eee eeeeeee eee eeeeeee ee −88°M eee 88 e. Mee eeeeeeee eee eeeeeeee eeee 8.8 M MMe ee MeMM (8.888 eM), eee eeeeeee eee eeeeeeeeeeee ee 88 Meee, eee e eeee ee eeeeeeeee eeeee/Me8M (8:8; 88 eM) eee eeeee. Mee eeeeeeeeeeee (M)-eeeeeeee(eeeeeeeeee-8-ee)eeeeeeee eeeeeeeeeeeee [8.888 e, (88%)] eee eeeeeeeee ee eeeeeeeeee. Mee eeeeeeee eee eeeeeee eeee Me8M (88 eM), eeeeee eeee eee. ee Me8MM8 (8×88 eM) eee eeeee (8×88 eM), eeeee (MeMM8), eee eeeeeeeeeeee ee eeee (M)-8,8,8-eeeeeeeee-8,8-eeeeeeeeeeeee-8-ee (‌88‌, M8 = e-Me) ee e eeeeeeee, eeeeeeeee eeeee eeeeeeeeee 88 ee% eeeeeee; eeeee: 8.88 e (88%, eeeeeeeee eee eeee ee eeeeeee); 88% ee.

Me e eeee ee (M)-8,8,8-eeeeeeeee-8,8-eeeeeeeeeeeee-8-ee (‌88‌, M8 = e-Me; 8.88 e, 88.8 eeee) ee MMM (88 eM) ee 88°M eeeee eeeeeeee eeeeeeee eeeeee 88 e eee eeeee e 88°M eeee ee MeMM (8.88 e, 888 eeee) eee MeM8 (8.88 e, 88.8 eeee) ee M8M (888 eM). Meeee 8 eee, eee eeeeeee eee eeeeeee ee 88°M eee 88 e. Mee eeeeeee eee eeeeee eeee Me8M, eeeee eee eeeeeeeee eeee 8% ee MeMM (88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeeeeee eeee eeeee MM8MM8 ee 8°M eee eeeeeeeee eeee MeMMe (8×88 eM). Mee eeeeeee eeeeee eeee eeeeeeee eee eeeee (MeMM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMM 88:8 e/e) eeeeee ‌88‌ (M8 = e-Me); eeeee: 88%; [α]M88 −88.8 (e 8.88, MMMe8); MMMM (eeee) ν̃eee: 8888–8888, 8888, 8888 ee−8.

eee/eeeee-8-(8-Meeeeeeeee)-M,M-eeeeeeee-8-[8-(eeeeeeeee)eeeee]eeeeeeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeeee eeee ee eeeeeeeee eeeeeeeee eee ee eeeeeeee eeeeeeeeeee ee eeeeeeeeeeee ee eeee eeeeee. Me ee e eeeeee eeeeeeee eeee eeeeeee ee eee eeeeeee eeeeeee eeeeee.

Me e eeee ee eee/eeeee-8-{8-[8-(eeeeeeeee)eeeee]-8-(eeeeeeeeeeeee)eeeeeeeeeee}eeeeeee (‌88‌; 8.88 e, 8.88 eeee) ee eeeee eeeeeee (MMMMMMM: eeeeeeeeee) eeee eeeee, ee eeeeeeee, 8 M MM8 ee eeeeeee (8.88 eM),[‌88‌] Me8M (8.88 e, 8.88 eeee), eee MMMM (8.88 eM, 8.88 eeee). Mee eeeeeee eee eeeeeee eee 8 e ee ee, eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/Me8M/MM8Me8 8:8:8; Me 8.88) ee eeee ‌88‌ ee e eeeeeeeee eee; eeeee: 8.88 e (88%).

Meeeeeeeeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee eeee ee eee eeeeeee ‌88‌ (88 eeee) eee MMMM (8 eeee) ee eee MMM (88 eM) eeeee eeeee eee eeeee Me8M (8.88 eM, 88 eeee) eeeeeeee ee Me8MMe (8.88 eM, 88 eeee). Mee eeeeeee eee eeeeeee ee ee eee 8 e, eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeee eeee eeeeee/MeMMe (8:8; 888 eM) eee eeeeeeee eeeeeee e eee ee eeeeeeeee eeeeeee eee Meeeee. Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee eee eeeeeeeeeee ‌88‌, eeeee eee eeee eeeeeee eeeeeee eeeeeeeeeeee; eeeee: 88 ee >88%.

(M)-(8-Meeee-8-eeeeeeeeeeee)eeeeeee [‌88‌, M8 = (MM8)8Me; M8 = Me; M8 = Me]; Meeeeee Meeeeeeee:[‌88‌]

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

Me e eeeeeee eeee ee (M)-8-eeeeee-8-eeeeeeeeeeee-8-ee eeeeeeeeeeeeeeeeeee [‌88‌, M8 = (MM8)8Me; M8 = Me; M8 = Me; 888 ee, 8.88 eeee] ee eee MMMe8 (8.8 eM) eeeee ee eeeee eeeeeeeeee eeee eeeee 8-eeeeeeeeeeee-8,8-eeeeeee (‌88‌; 8.88 eeee) eee ee −88°M MMMM8 (88.8 μM, 88.8 ee, 8.88 eeee). Mee eeeeeee eee eeeeeee ee eeee ee ee eee eeeeeee eee 88 e. Meeeeeeeeeee ee eeeeeeeeeee MMM eeee ‌88‌ [M8 = (MM8)8Me; M8 = Me; M8 = Me]; eeeee: 88.8 ee (88%).

References