Science of Synthesis

Claver, C.; Peñafiel, I.; Urrutigoïty, M.; Kalck, P., Science of Synthesis: Catalytic Reduction in Organic Synthesis, (2018) 2, 305.

In 1996, the first asymmetric transfer hydrogenation of imines was reported, using half-sandwich ruthenium–N-tosyl-1,2-diphenylethane-1,2-diamine (TsDPEN) complex ‌43‌ as catalyst (‌Scheme 19‌).[‌68‌] Since then, a large number of articles and reviews on the use of N-sulfonylated 1,2-diamines as chiral ligands in asymmetric transfer hydrogenation of ketones and imines have appeared.[‌7‌,‌69‌–‌75‌] A variety of imines have been successfully reduced in high yield and enantioselectivity using the formic acid/triethylamine azeotrope in the presence of Noyoriʼs ruthenium catalyst ‌43‌.

‌Meeeee 88‌ Meeeeeʼe Meeeeeeee Meeeeeee[‌88‌]

Me e eeeeeee eeeeeeeeeee, eee eeeeeeeeee eeeeeeee eeeeeeeeeeeee ee eeee eeeeeeeeeee eeeeeee eeeeeeeeeeeeeee-eeeeeeeeeee eeeee eeeeeeeeee eee eeeeeeee eeeee eeeeeeeee–M-eeeee-8,8-eeeeeeeeeeeeee-8,8-eeeeeee eeeeeee ‌88‌ eee eeeeee eeeeeee ee eee eeeeeeee eeeeee (‌Meeeee 88‌).[‌88‌] Mee eeeeeeee eeeee eeeee eeeee eeee eeeeeeeeee eeeee eeeee eee eeeeeeeeeeeeeeeee ee eeeeeee eee eeeeeeeee, eeeeeeeeeeee. Meeeeeeee eeeeeeee ee eeeeee eeee-eeeeeeeeeee α-eeeeeeeeeeeeeee eeeeee ‌88‌ eeee eeeeeeee ee eeee eeeeee eee eeeeeeeeeeeeeeeeeeee (88–88% ee), eeeeeee eee eeee ee eee eee ee eeee eeeeeeeeee ee eeeeeeee eeeeee eeeeeeeeeeeeeee-eeeeeeeeeeeeee eeeeee.

‌Meeeee 88‌ Meeeeeeeee Meeeeeee Meeeeeeeeeeee ee Meeeeee Meeeeeeeeeeeeee-Meeeeeeeeee Meeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeeeeee eeee eeeeeeeeee eee eeeeeeeeeeeee eee eeeeeeee eeeee eeeeeeeee–M-eeeee-8,8-eeeeeeeeeeeeee-8,8-eeeeeee eeeeeeeee, eeeee ee e eeeeee ee ee eeee ee eeeee eeee eeeeeee eeeee eeeeeeeeeeeeeee eeeeeeee eeeeeeeeee eee ee eeee eeee eeeeeeee. Meee eeee eee, eeeeeeee eee eeee eeeeeeeee eeeeee eee eee ee eeeee-eeeeeee ee eeeeeeeeeee eeeeeee eeee ee ‌88‌–‌88‌ eee eee eeeeeeeee ee eeeeee eeeeee (‌Meeeee 88‌). Meee eeeeee eee eeeeeeeeeeeeeeeeeeee eee eeeeee ‌88‌ eee ‌88‌ eee eeeeeeee ee eee eeeeeeeee ee eee eeeeeeeeeeeee eeeeee eeeeee ee eeeee eeeee eeeeee eeeeeee ee eee eeeeeeee eeeeee eee eeeee(eeeeeeeee)eeeeeeee eeeeeee ee e eeeeeeeeee ee eeeeeeeeeee eeee eee eeeee-eeeeeee e,e′-eeeeeeeeeeee M-eeeee-8,8-eeeeeeeeeeeeee-8,8-eeeeeee eeeeee ‌88‌, ee eee eeeeeeee ee eeeeeeee(e-eeeeee)eeeeeeeee(MM) eeeee ee eeeeeeee eeeeeeeee. Meeeeee, eee eeeeeeee ee eeeeeeee eeeeeeeeeeeee ee eeeeeee eeeeee ee eeeee eeeeeeee ee ee eeeeeeee ee eeeeeeee eeeeeeeeeeeee.[‌88‌]

Meeeeee eeee eeee eeee ee eeeeeee eeeeeeeeee eeeeeeeee eeeeeeeee eeeeeee eee eeeeeeeeeeeeee ee eee eeeeeeeee ee eeeeeeeee eeeeeeee. Meeee eee eeeeeee eeeeee eee eeeeeee M-eeeeeeee-8,8-eeeeeeeeeeeeee-8,8-eeeeeee eeeeeee eee eeeeeeeee(MM) eeeeeeeee eeee eeee eeee eeeeeeee, eee eeeeee eee eeeeeeeeeee M-eeeeeeee-8,8-eeeeeeeeeeeeee-8,8-eeeeeee eeeeee ‌88‌ eeeeeeee eee eeeeeee eeeeeeeeee, eeeeeeeeeeeeeeeeee, eee eeeeeeeeeee.[‌88‌] Mee eeeeeeee(e-eeeeee)eeeeeeeee(MM) eeeee/‌88‌ eeeeeeeee eeeeee eee ee eeeeeeee ee ee eee eeeee, eeeeeeeee eeeeee eeeee ‌88‌ (M8 = Me) eeee ee eeeeeeee ee eee eeeeeeeeeeeeeeeeee (88–88% ee) eeeee eee eeeeee eeee/eeeeeeeeeeeee eeeeeeeee ee eeeeeeeeeeeeeee. Me e eeeeeee eeeeeeeeeee, eee ee eeeeee eeeeeeeeee eeeeeeee, eee M-eeeeeeee-8,8-eeeeeeeeeeeeee-8,8-eeeeeee eeeeeeeeee ‌88‌ eee eeee eeeeeeeeeee eeee eeeeeeee eeeeeeeeee eeeeee eee.[‌88‌] Mee eeeeeeeee eeeeee eeeeeee eeeeee eeeeee ee eeee eeeeeeeeeeeeeeeeeeee, eee eeeee eeee eeeeeeeee eee eeeeeeeeee eeeeeeeee eeeeeee (ee eeeeeeeeee eeee ee eeeeeeee eeeeee) ee ee eeee eeeee eeeeeee eeee ee eeeeeeeeeeeeeeeeee (ee ee 88% ee eee eeeeee eeeeee). Meeeeeee eeee eeeeeeeeeee eee eeeeeeeeeeeeeeeeeeee eeee eeee eeeeeeeee eeeee eeeee eeeeeeeeee eeeeeeeee, ee eeeeee ee eeeee eeee eeee eeeeeeeee eeeee eeeeeeeeeee eeeeeeeee eee eeeeeeeeeeeee eeeeee eeee eeee eeeee eeeeeeeeeee eeeeeeeeeeee eee eeeeeeee.

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

‌Meeeee 88‌ Meeee-Meeeeee eee Meeeeeeeeee Meeeeee Meee ee Meeeeeeeee Meeeeeee Meeeeeeeeeeee[‌88‌–‌88‌]

‌Meeeeeeeeee 88‌

‌Meeeeeeeeee 88M‌

Meeee eeeeeeeee eeeeeeeee eeeeeee eeee eeeeeeee eee eeeeeeeeeeeeeeeeee. Mee eeeeeeee, eee eeeeeeeee eeeeeee eeeeeeee eeee eeeeeeee(e-eeeeee)eeeeeeeee(MM) eeeee eee (8M,8M)-8-eeeee-8,8-eeeeeee-8M-eeeee-8-ee (‌88‌) ee ee eeeeeeeee eeeeeeee eee eee eeeeeeeeee eeeeeeee eeeeeeeeeeeee ee (M)-M-eeee-eeeeeeeeeeeee eeeeeeeee ee eeeeee-8-ee (‌Meeeee 88‌). Mee eeeeeeeeeeeee eeeeee eeeeeee eeeeee eee eeeeeeee eeee eeeeeeeee eeeeeeeeeeeeeeeeeeee (ee ee 88% ee) eee eeeeeeeeeeeeeeeeee eeeeeeeee ee eee eeeee eeeeeeee ee eeeeeee ee eee eeeeeeee eeeee eeeee eeee eeeeee eeeeeeeeee.[‌88‌]

‌Meeeee 88‌ Meeeeeeeee Meeeeeee Meeeeeeeeeeee ee (M)-M-eeee-Meeeeeeeeeeee Meeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Mee eeeeeeeee ee e eee eeeee ee eeeeeeeeeeeee eeeeeeee eeeeeeee eeee ee eeeeeeeeeee eeeeeeeeeeeeeeee eeee eeeeeee eeeeeee [(M)-(+)-eeeeeeee] eeeeeeeeeee ee eeeeeeeeeee eeeeeeee. Meee, ee M-eeeeeeeeeeeeeeeeee ee eeeeeeee, eeeeeeee ee eeeeee eeeee eeeeeeeee eee eeeeeeeee eeeeeee eee eeeeeeeeeeeee eeeeee eeeeee, eeeee eee eeee ee eeeeeee ee eee eeeeeeeee eeeeeeeee ‌88‌ eee ‌88‌ eee eeeeeeeeee eeeeeeee eeeeeeeeeeeee ee eeeeeee eee eeeeee, eeee ee ee 88% ee eeeeeeee eee eee eeeeeeeeeeeeeee ee eeeeeeee eeeeeeeeee eeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee Meeeeeeee ee Meeeeeeeeeeee Meeeeee Meeeeee Meee ee eee Meeeeeeeee Meeeeeee Meeeeeeeeeeee ee Meeeeee eee Meeeee[‌88‌]

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

‌Meeeee 88‌ Meeeeeeee-Meeeeeeee Meeeeeeeee Meeeeeee Meeeeeeeeeeee ee Meeeee Meeee Meeee eee Meeeeeeee Meeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeeeeee	M	Meeee (%)	ee (%)	Mee
‌88‌	M(MMe)8	88	88	[‌88‌]
‌88‌	M(MMe)8	88	88	[‌88‌]
‌88‌		88	88	[‌88‌]
‌88‌	M(MMe)8	88	88	[‌88‌]
‌88‌	M(MMe)8	88	88	[‌88‌]

Meeeeeeeeeee Meeeeeeee

M-Meeeee-8-eeeeeeeeeee-8-eeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

Meeeeeeeeee ee eee eeeeeee-eeeeeeeeeee eeeeeeee: M 88-eM, eeeee-eeeeeeee eeeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee eeeeeee eeee eeeeeee-eeeeeeeeeee eeeeee ‌88‌ (8.888 eeee ee eeeeeee), {MeMe8(e-eeeeee)}8 (8.888 eeee), eee MeMM (8 eM) eeeee eeeee. Meeee eeeee eeeeee–eeee eeeeee eeeee eee M8, eee eeeeeee eee eeeeee ee 88 °M eee 8 e. Mee eeeeeee eee eeee eeeeeee eeeee eeee eeeeee ee eeeee eee eeeeeee-eeeeeeeeeee eeeeee eeeeeeee ee e eeeeeee eeeee, eeeee eee eeee eeeeeeee ee eee eeeeeeee eeeeeeeeeeeee.

Meeeeeee eeeeeeeeeeeee: M 88-eM, eeeee-eeeeeeee eeeee eeeeeeee eeee e eeeeeeee eeeeeee eee eee eeeeeee eeee M-eeeeee-8-eeeeeeeeeee-8-eeeee (888 ee, 8.88 eeee), eee eeeeeee-eeeeeeeeeee eeeeee eeeeeeee (88 µeee Me), ee eeeeeeeeee eeeeeee ee MMM8M/Me8M (8:8; 8.8 eeee MMM8M), eee MM8Me8 (8.8 eM) eeeee eeeee. Meeee eeeee eeeeee–eeee eeeeee eeeee eee M8, eee eeeeeee eee eeeeeee ee 8 °M eee 88 e. Mee. ee Me8MM8 eee eeeee eee eee eeeeeee eee eeeeeeee eeeeeee e eeeee eeeeee. Mee eeeeeeee eee eeeeeeeeeeee eee eee eeeeeeee eeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:8) ee eeee eee eeeeeee ee e eeeeeeeee eeeeee; eeeee: 88% (eeeeeeeeee ee MMM eeeeeeeeeeee); 88% ee. Mee eeeeeeeeeeeee eeeeeeee eeeeeeeee ee ee eee 88 e eeee eee eeeeeee ee 88% eeeee (ee MMM) eee 88% ee.

References