Science of Synthesis

Schneider, C.; Sickert, M., Science of Synthesis Knowledge Updates, (2017) 3, 371.

Chiral phosphoric acids based on the 1,1′-bi-2-naphthol backbone were introduced independently into asymmetric catalysis by the groups of Akiyama and Terada in 2004.[‌90‌,‌91‌] Since this breakthrough, a broad range of enantioselective imine addition reactions have been reported, proving that such chiral Brønsted acid catalysts are able to facilitate effective asymmetric inductions by chiral contact ion pairs generated in situ.

Me 8888, Meeeeee eee ee-eeeeeee eeeeeeee ee eeeeeeeeee Meeeeee eeeeeeee eeeeeeeee ee eeeeeee eeeeee eeeeeeeeeeee eeee ‌888‌, eeeee eeeeeeeeeeeee ‌888‌ (M8 = MM8e-Me) eee (eeeeeeeeeee)eeeeeeeeeeee ‌888‌ [M8 = M(M)(MMe)8] eeee eeeeeeeeeeee eeee ee eeeeeeeeeeee eee eee eeeeeeee eeee eeee-eeeeeeeeeeeeee-eeeeeeeee eeeeee ‌888‌ (‌Meeeee 88‌).[‌88‌] Meee eeeee eeeee, eee eeee eeeee eee eeee ee eeeeee eeeeeeeeeeee eeeeeeeeeee eeeeee β-eeeee eeeeeeee ee eeeeeeeee eee eeeeeeee ee eee eeeeeeeeee ee eee eeeeeeeeeeee eeeeeeeeeee 8-eeeee eeeeeeee ‌888‌ (M8 = Me).[‌88‌] Mee eeeeeeee ‌888‌ eee eeeeeeee ee eeeeeeeeeeee eeee eeeeeeeeeeeeeeeeeeee (ee ee 88% ee) eee eeeeee (ee ee 88%). Meeeeee eeeeeeeeeeee eeeeeeee eee eeeeeeeeeeeeeee eeee eeeeeeeee eeeeeeeeee eeeeeeeeee ee eee eeeeeeee eeee eee eeeeeee eeee-eeeeeeeeeeeeee-eeeeeeeee eeeeee eee ee eeeeeeee. Meeeeeeeeee, eee eeeeeeee β-eeeee eeeeeeee eee ee eeeeee eeeeeeeeeee eeee eeeeee α-eeeee eeeee (e.e., ‌888‌), eeeeeee eeeeeeeee eee eeeeeeeeeeee eeeeee, ee eeeeeeeee eeeeeeee ee eee eeeee eeeeee eeeee eeeee ee eeeeeeee.

‌Meeeee 88‌ Meeeeeeeee Meeeeee Meeeeeee ee Meeeeeeeeeeee, (Meeeeeeeeee)eeeeeeeeeeee, eee Meeeeeeeeee Meeeeeee Meeeeeeee ee e Meeeee Meeeeeeeeeee Meee[‌88‌,‌88‌]

‌Meeeeeeeeee 88‌

M8	M8	Meee (e)	ee (%)	Meeeee (%)	Mee
MM8e-Me	Me	88	88	88	[‌88‌,‌88‌]
MM8e-Me	8-MeM8M8	88	88	88	[‌88‌,‌88‌]
MM8e-Me	8-eeeee	88	88	88e	[‌88‌,‌88‌]
M(M)(MMe)8	Me	88	88	88	[‌88‌,‌88‌]
M(M)(MMe)8	8-eeeee	88	88	88	[‌88‌,‌88‌]
Me	Me	88	88	88	[‌88‌]
Me	8-Mee	888	88	88	[‌88‌]
Me	8-Mee	88	88	88	[‌88‌]
Me	8-eeeeeeee	88	88	88	[‌88‌]
Me	8-MeM8M8	88	88	88	[‌88‌]
Me	8-MeMM8M8	88	88	88e	[‌88‌]
Me		88	88	88	[‌88‌]
Me	8-eeeee	88	88	88e	[‌88‌]

e Meeee 8.88 eeee ee eeeee ‌888‌.

e Meeeeeee eee ee −88 °M.

Me 8888, Meeeeeee eee ee-eeeeeee eeeeeeeeeeee eeee eeeeee eee(eeeeeeee) eeeee (e.e., ‌888‌) ee eeeeeeeeeee eeee eeeeeeeeee eeeeeeee eeeeeeeee (e.e., ‌888‌) eee eeeeeeee eeeeeeeee eee eee eeeeeeee ee 8,8-eeeeeeeee ‌888‌, eee eee eee eeeee eeeeeeee, eeee eeeeeeee eeeeeeeeeeeeeeeee-eeeeeeeee eeeeeeeee ‌888‌, eeeeeeeee eee Meeeeee eeeeeeee ‌888‌ ee eeee eeeeee (ee ee 88%) eee eeeeeeeee eeeeeeeeeeeeeeeeeeee (ee ee 88% ee; ‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeeee Meeeeee Meeeeeee ee 8,8-Meeeeeeee Meeeeeeee ee e Meeeee Meeeeeeeee 8,8′-Meeeeeeeee-8,8′-eeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

M8	M8	Me8	ee (%)	Meeee (%)	Mee
Me	Me	Me	88	88	[‌88‌]
Me	Me	8-Mee	88	88	[‌88‌]
Me	Me	8-Mee	88	88	[‌88‌]
Me	Me	8-MeMM8M8	88	88	[‌88‌]
Me	Me	8-MeM8M8	88	88	[‌88‌]
Me	Me	8-eeeeeeee	88	88	[‌88‌]
Me	Me	8-eeeeeee	88	88	[‌88‌]
Me	Me	Me	88	88	[‌88‌]
Me	Me	Me	88	>88	[‌88‌]
	Me	Me	88 (eee)/88 (eeee)	88e	[‌88‌]

e Meeee (eee/eeee) = 88:88.

Mee eee ee eee eeeeeee ee eeee eeeeeeeeeeeeee eeee ee eee eeeeeeeeee eeeeeee ee eeeeeee eeee eee Meøeeeee eeeeeee eee eeeeeeeee ee eee eeeeeeee ee eeeeeeeeeeee ee ‌888‌ eeee eeeeeee eeeeee eeee ee 8,8-eeeeeeeeeeeeeeee (‌888‌), eeeeeeeee eee eeeeeeee eee eeeeee eeeeee ee eeeeee 8,8′-eeeeeeeeeeeee eeeeeeeeee-eeeee eeeeeeeeee eeeee. Me eeeeeeee, eee(eeeeeeee) eeee ‌888‌ ee eeeeeeee ee ee ee eeeeeeeeeee eeee eeeeeeeee ‌888‌ eee ‌888‌, eeeeeeeee ee eee eeeeee ee eeeeeee eeeee (‌Meeeee 88‌). Meeee ee eeeeeeeeeeee eeeeeee, eee eeee eeeeeee eee eeeeeeee eeeee e 8:8 eeeee ee eeeeeee eeeee/‌888‌, eeeeeeeeee eeee eeeeeee ‌888‌ ee eeeeee eeeeeeee ee ee eeeeeeeee eeeeeeeee eeeee. Meee eee eeeeeeeeeeeeeeeeeeee eee eeeeeeee eeeee eeeee eeeeeee ee 8,8-eeeeeeeeeeeeeeee (‌888‌). Mee eeeeeeeeee eee eeeeeeeeee ee eeee eeeeeee ee eeeeeeeeeee ee eee eeeeeeeee eeeeeeeee eeeee; eeeeeee eeeeeeeeeeee ee eee eeeeeeee eeee ee eee eeeee ‌888‌ ee eeee ee eeeeeeeeeeeee ee eee eeeeeeee ‌888‌ eee ee eeeeeee, eeeeeee eeee ee eeeeeeee eeeeeeeeee eeeeeee (‌Meeeee 88‌).

‌Meeeee 88‌ Meeeeeeeeeeeeee ee Meeeeeeee ee Meeeee Meeeeeeeee 8,8′-Meeeeeeeee-8,8′-eeeeeeeeeeee[‌88‌]

Mee eeeeeeeeeee ee eee eeeeeeeeee ‌888‌ ee eeeeeeeeee Meeeeee eeeeeeeee eeeeeeeee ee eeeeee eeeeeeeeee eeee ‌888‌ eee eeeeeeeee ee Meeeeeee eee ee-eeeeeee ee 8888.[‌88‌] Meee eeee 8 eee% ee eee eeeeeeee, eee eeeeeeee ‌888‌ eeeeeeeeee eee eeeeeeeeeee eeeeeeeeeee eeeeeee eee eeeeeeee ee eeeeeeeee eeeeeeeee- (ee ee ee >88:8) eee eeeeeeeeeeeeeeeeeeee (ee ee >88% ee; ‌Meeeee 88‌). Meeeeeeeeeeee, eee eeeeeeeeeee eee eeeee ee eee eeeeeeee eeeeee ee eee eeee ee eee eeeeeeeeeeee ee eee eeeeeeee eeeeeeeeee eeeee ee eee eeeeeeee, ee eeee M-eeeee-eeeeeeeee eeeeeeeee ‌888‌ eee eeeeeeeee ee eee 8,8,8-eeeeeeeeeeeeeeeeee-eeeeeeeeeee eeeeeeeeee eeee eeeeeeee ‌888‌. Meeeeeee eeeeeeeee eee eeeeeeeeee ee eeeeeeee eeeeeeee eeeeeeee, eeee eeeeeeeeeeeeeee eeeeeeeee ee eee eeeee, eeee, eee eeee eeeeeeeee. Mee eeeeeee eeee eeeee ee eeeeeeeeeee eeeeeeeee eeeeeeeee eeee eeeeeeeee eeeeeeeee; eeeeeee, eee eeeeeeeeeee ee eee eeeeeee M-eeeee eeeeeeeeeee eee eee eeeeeeeeee.

‌Meeeee 88‌ Meeeeeeeee Meeeeee Meeeeeee ee Meeeeeeeee Meeeeeeee ee e Meeeee Meeeeeeeee Meee[‌88‌]

‌Meeeeeeeeee 88‌

Meeeeeeeeeee Meeeeeeee

Meeeee (M)-(8-Meeeee-8-eee-8-eeeeeeeeeee)eeeeeeeee (‌888‌, M8 = M8 = Me; M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeeeeeeee ee eeeeeeeee ee eeee eeeeee eee eeeee, eee ee eeeee ee eeeeeee eeee eeee eee ee eeeeeee.

M eeee-eeeee Meeeeee eeee eee eeeeeee eeee (M)-8,8′-eeeeeeeeee-8,8′-eeeeeeeeee eeee (‌888‌; 8.8 ee, 8.8 µeee, 8 eee%) eee 8,8-eeeeeeeeeeeeeeee (‌888‌; 8.8 ee, 8 µeee, 8 eee%) eeeee M8. MeMM (8 eM) eee eeeee, eee eee eeee eee eeeeeee ee ee eee 88 eee. Mee eeeeeeee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eeee MeMM8 (88 ee, 8.88 eeee, 8.8 eeeee) eee MM8Me8 (8.8 eM) eeee eeeee. Mee eeeeeeeeee eee eeeeeee ee ee eee 88 eee eee eeeeee ee 8 °M. Meeeee (M)-eeeeeeeeeeeeeeeeeeee (‌888‌, Me8 = Me; 88.8 ee, 8.888 eeee, 8.8 eeeee) ee MM8Me8 (8.8 eM) eee eeeee eee eeeeeee, eee eeee eeeeeeeeeeeee (‌888‌, M8 = M8 = Me; 88.8 ee, 8.88 eeee, 8.8 eeeee) ee MM8Me8 (8.8 eM) eee eeeee eeee 8 e (e eeeeeee eeee ee eeeeee ee eeeeeeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 8 °M eee 88 eee (MMM eeeeeeeeee). Mee. ee MeMMM8 (88 eM) eee eeeeee eeee eee eeeeeee, eee eee eeeeeee eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeeee eeee eeeeee eeee eeeee (88 eM), eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:8); eeeee: 88 ee (88%); 88% ee; [α]M88.8 +88.8 (e 8.8, MMMe8).

M-{(M)-[(M)-8-Meeeee-8-eee-8-eeeeee-8,8-eeeeeeeeeeeee-8-ee](eeeeee)eeeeee}eeeeeeeeee­eeeeeeee (‌888‌, M8 = Me; Me8 = Me); Meeeeee Meeeeeeee:[‌88‌]

M eeeee-eeeee eeeee-eee eeee eee eeeeee eeee M8 eee eeeeeeeeeeee eeeeeee eeee 8-Å eeeeeeeee eeeeee (88 ee), eeeeeeeee ‌888‌ (M8 = Me; 88 ee, 8.8 eeee, 8.8 eeeee), eee eeeeeee (8 eM). Meeeeeeeee eeee ‌888‌ (8.8 ee, 8 µeee, 8 eee%) eee eeeee, eeeeeeee ee (M)-M-eee­eeeeeeeeeeeeeeeeeeeeeeeeee (‌888‌, Me8 = Me; 88 ee, 8.88 eeee, 8.88 eeeee). Mee eeeeeeee eee eeee ee ee eee eeeee M8 eee 88 e. Mee eeeeeee eee eeee eeeeeee eeee MM8Me8 (88 eM) eee eeeeee eeee eee. ee MeMMM8 (8 eM). Mee eeeeeee eeeee eee eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8); eeeee: 88.8 ee (88%); ee >88:8; >88% ee.

References