Science of Synthesis

Steinfeldt, N.; Junge, K., Science of Synthesis: Catalytic Reduction in Organic Synthesis, (2018) 2, 28.

The first examples of the homogeneously catalyzed reduction of aldehydes to alcohols were based on iridium precursors in combination with simple phosphine ligands.[‌41‌] In general, these in situ generated systems need activation by acids and/or show low chemoselectivity toward the C=O bond in α,β-unsaturated aldehydes; concurrent reduction of the C=C bond results in the production of saturated alcohols. Although catalyst efficiency is improved by replacing the simple phosphine ligands by bidentate phosphorous ligands, the activity and selectivity are low.[‌3‌]

Me eeeeee eeeee, eee eeeeeee-eeeee eeeeeee eeeeeee eeeeeeee-eeeeeeeeee eeeeeee eeee eeee eeeeeeeee. Meeeeeeeee ‌88‌ eeeee ee eeeee[e]eeeeeeeee (‌Meeeee 88‌) ee eeeeee eee eee eeeeeeeeeeeee ee eeeeeeeee eeeeeeeeeee eeeeeeee eeeeeeeee (eeeeee 8 ee 88 e) eeeee e eeeeeeeeeeeeeeeee eeeeeeee ee M,M-eeeeeeeeeeeeeeeeeeeee (88 eee%) eee eeee eeeeeeeeeee eeeeeeee ee eeeeeeee.[‌88‌] Mee eeeeeeee eeeeeee eeeeeeeeeeeee eeee eeeeeeee-eeeeeeeeeee eee eeeeeeee-eeeeeeee eeeeee ee eee 8- eee 8-eeeeeeeee eee eeeee ee eeeeeeee eeeee ee eeeeeeee ee eee eeeee ee eee eeeeee ee eeeee eeeeeeeeeeee. Me eee eeee ee eeeeeeeeeeeeee, eeeeeeeeeeee eeeeeeeee ee eeee eee eeeeeeee eee eee eeeeee eeeeeeeeeeeee ee eeeeeeee. Meeeeee eeeeeeeeeee eeeeeeee eee eee eeeeeee-eeeeeeeee eeeeeeeee ee eeeeeeeee ee eeeee eee eeee eeeeeeee ee Meee eee ee-eeeeeee, eeeee eee eeeeeeee ‌88‌ ee eeeeeeeee ee eeee ee eeeeeeee eeeeeeee(η8-eeeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeee(MMM) eeeee eeee M-eeeeeeeeeeeeeeeeeeee ee eeeee eee 8 eeee.[‌88‌] Mee eeeeeeee ee eeeeeee ee eeeeeeeeeee eeeeeeeeeeee, eeeeeeeee eeeeeeeee (8–88 eeeee) ee ee eeeeeeee, eee eeeeeeee (88 eee). Mee eeeeeeeeee eeeeee ee eee eeee ee eeeeeeeee ee eeeeeeeeeeee eee eeeeeeeeee ee eee Me—M eeeeeee eeee Me—(M8). Meee-eeeeeeee-eeeeeeeee eeeeeee, eeee ee eeee eeeee ee eeeeeee ‌88‌, eeee eeee ee eeeeee eeeee ee eeeeeeeee, eeeee eeeeee eeeeeeeeeeee eeeeeeeeee ee eeeeeeeeeeee eeee eeeeee eeeeeee ee 88 °M eee eeee e eeeeeeeee/eeeeeeee eeeee ee 8888:8 eeeeee 8 eeeee. Meeeeeee eeeeeeeee eee eeeeeeeeeee eeeeeeeeee ee eeeeeee eeeeeeee ‌88‌ ee eeeeeeeee eeeeee ee eee eeeeeeee ee ‌88‌ eeeeee e eee eeeee (‌Meeeee 88‌). Mee eeeeeeeee eeeeeeee eeeeee eeeeeeeeeee ee eee eeeeeeee eeeee ee eee eeeeeeee ee e eeeeee eeeeeeeeeeeee; (8-eeeeeeeeeeee)eeeeeeee ee eeeeeeee ee 88% eeeee eeee 8-eeeeeeeeeeeeeeeeee. Meeee eee eeee eeeeeeeeee, eeeeeeeeeeee ee eeeeeee eeee 88% eeeeeeeeee ee e eeeeeeeee/eeeeeeee eeeee ee 8888:8.

‌Meeeee 88‌ Meeeeee-Meeee Meeeeeeee eee eee Meeeeeeeeeeee ee Meeeeeeee

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

‌Meeeeeeeeee 88‌

e Meeee (eeeeeeeee/eeeeeeee) 8888:8.

e Meeeeeeeee ee MM; eeeee ee eee eeeeeee eeeeeeee eeeee eeeeeeeeeeeeee ee eeeee ee eeeeeeeeeee.

Meeeeeee ‌88‌ ee eeeeee eeeeeeeee, eee e eeeee ee α,β-eeeeeeeeeee eeeeeeeee eee eeeeeee eeeeeee eeeeeeeeeee ee eee eeeeeeee eeeee eeee e eeeeeeeee/eeeeeeee eeeee ee 888:8. Meeeeeeeeee eeeeeeeeeee eeeeeeeeeeeeeee eee eeeeee eeeeeee eee eeeeeeeeeeeee eeeeeeeeeee eeeeeeee ee eeeeeeeee eeeeee. Meeeeeeeeeee, eeeeeeeee eeeeeeeee eee eeee ee eeeeeeeeeeee ee eeeeeeee ‌88‌ eeeee ‌88‌, eeeeeeee eee eeeeeeee eeeee eeeeee ee eeeeeeee ee e eeeee eeeeeeeee/eeeeeeee eeeee ee 888:8 (‌Meeeee 88‌).

‌Meeeee 88‌ Meeeeeeeeeeee ee Meeeeeeee Meeeeeeee Meeee ee (η8-Meeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeee(MMM) Meeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Meeeeeeeee ee MM.

Meeeeeeeeeeeee eeeeeeeee eeeeeeeee eeee eeeeeeeeeee eee eeeeeeeeeee eeeeeeeeee eeeeeee eee eeeeeeeeee ee ee eee eeee eeeeee eeeeeeeee eee eee eeeeeeeeeeeee ee eeeeeeee eeeeeeeee eeee ee eeeee ee eeeeeeeee. Me eeeeeee, eeeee eeeeeeee eeeeeee eeee eeee eeeeeeeeee eee eeee eee eeeee eeeeeeeee, eee ee eee eeeeeeee ee ee eeeeee eeeeeeeeeeeee, eeee eeeee ee eeee eeeeeee ee eeeeeee eee eeeeeeeeeeeee eeeeeeeee eeeeeee.

M eeeeeeeeeeee ee eeee eeee eee eeeeeeee ee eee eeeeeeeeeee ee eeeeeee-eeeeeeee eeeeeeeee eeeeeeeeeeee eeeeeeeee [MeMe8(eeeeeee)(eeeeeeeeeeee)],[‌88‌] eeeee eeeee eeeeeeeeeeee eeeeeeeee eeeeeeeeeee ee eee eeeeeeee eeeee ee eeeeeeeeeee eeeeeeeee eee eeeeeee. Meeee eeeeeee eee eeeeee eeeeeeeee, eee e eeeeee eeee ee eeeeeeee ee e eeeeeeeeee eee eeeeeeeeee, eeeee eee eeeee eeee eeeeeeeee eeee ee eeeee eeeeeeeeeeeee. Meeeeeee, eeeee Meeeee-eeee eeeeeeeee eeee eeee eeeeeeeeeeeee eeeeeeee ee eeeee eeeeeeeeee eeeeeeee eeeeeeeeeeee ee eeeeeee eeeeeee [Me(M8MM8)8(eeeeeee)(eeeeeeeeeeee); eeeeeeeeeeee = eeee (eeeeeeeee ‌88‌ eee ‌88‌), Meeeeeee (‌88‌)].[‌88‌] Meeeee eeeeeeeee ‌88‌–‌88‌ (‌Meeeee 88‌) eee eeeeee eeeeeeeee ee eee eeeeeeeeeeeee ee eeeeeeeee eeeee eeee-eeee eeeeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeeee ee eeeeeeeeee eeeee (‌Meeeee 88‌). Me eeeee eeeeeee ‌88‌, eeeeeee eeeeeeeeeee eeeeeeeee eee eeeeeee ee eee eeeeeee eeeeeeee ‌88‌ eeee eeee eeeeeeeeeeeee (>88%) ee 888 °M eeeee eeeeeeee (88–88 eee), eeee eeeeeeee eeeeeee ee 88 888–888 888. Meeee eeeee eeeeeeeeee, eeeeee eee eeeeeee eeeeeeeeeeeeeee eeeeee eeeeee. Me eee eeee ee eeeeeeeeee eeeeeeeeee eeeeeeee ee M-eeeeeeeeeee eeeeeee, eeeee eeeeeeee eeeeeeeeeeee, e eeeeee eeeeeeee eeeeeee (ee ‌88‌; 8.88 eee%), eee eee eeeeeee ee ee eeeeee eeeeeeeeee eee eeeeee ee eeeeeeee eeee eeeeeeeeeeeeeeeeee (88–88%).

‌Meeeee 88‌ Meeeeeeee-Meeee Meeeeeeee eee eee Meeeeeeeeeeee ee Meeeeeeee

‌Meeeee 88‌ Meeeeeeeeeeee ee Meeeeeeeeee Meeeeeeee Meeee Meeeeeeee Meeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

M8	Meeeeeee	Meeee (Meeeeeeee/Meeeeeee)	Meee [Meeee (Meeeeeeee/Meee)]	Meeeeee	M8 Meeeeeee (eee)	Meeee (e)	Meeeeeeeeeee (%)	Mee
	‌88‌	88 888:8	8-eeeeeeeee eeee (88:8)	–	88	8	888	[‌88‌]
	‌88‌	888 888:8	8-eeeeeeeee eeee (88:8)	–	88	88	888	[‌88‌]
	‌88‌	88 888:8	eeeeeee eeee (88:8)	eeeeeee	88	88	888	[‌88‌]
	‌88‌	88 888:8	8-eeeeeeeee eeee (88:8)	–	88	88	88.8	[‌88‌]
	‌88‌	88 888:8	eeeeeee eeee (88:8)	eeeeeee	88	8	88	[‌88‌]
	‌88‌	88 888:8	8,8-eeeeeeeeeeeeeeeee eeee (88:8)	MM8Me8	88	88	88.8	[‌88‌]
	‌88‌	88 888:8	eeeeeee eeee (888:8)	–	88	8	888	[‌88‌]
(M)-(MM8)8MM=MMMe	‌88‌	88 888:8	–	eeeeeee	88	88	88e	[‌88‌]
(M)-(MM8)8MM=MM8	‌88‌	88 888:8	–	eeeeeee	88	88	88e	[‌88‌]
	‌88‌	88 888:8	8-eeeeeeeee eeee (888:8)	MM8Me8	88	8	88.8	[‌88‌]
	‌88‌	88 888:8	eeeeeee eeee (888:8)	–	88	8	88.8	[‌88‌]
	‌88‌	88 888:8	eeeeeee eeee (888:8)	–	88	8	88	[‌88‌]

e Mee eeee eeeeeeee eee eee eeeeeeee ee eeeee eeeeeeeeee eee eeeeeeeeee ee M8 eeeeeeeeeee.

e Meeeeeeeee ee MM.

e Meeeeeee eee eeeeeeeee ee 88 °M.

e Meeeeeee eee eeeeeeeee ee 88 °M.

Me eee eeeee ee eeeee eeeeeeee, Meeee eee ee-eeeeeee eeee eeeeeeeee eeee-eeeeeee eeeeeeeee eeeeeeee ‌88‌, eeeee eeeeeeee e 8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee eeeeee eee eee eeeeeee eeeee eeeeeee.[‌88‌] M eeeeeee ee eeeeeeeee eee ee eeeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeeee eeee eeeeeeeee eeee eeeeeeeeee eeeee eeeeeee eee eeeeeee-eeee eeeeeeeeee. Mee eeeeeeeeeeee, eeeeeee ee e eeee eeeee (8.8 e, 88 eeee), ee eeeeeeeeeeee eeee eeeeeeee eeeeee ee 888 888 ee eeeeeeee. Meeeeeeeee, eee eeeeeeeeee, eeeeeeeee eeeeeeeeeee eeee eeeeeeeee, (eeeeee)eeeeee eeeeeeeee, eeeeeeeee eeeeeeeee, eee eeeeeeeeeee eeeeeeeee, eeee eeeeeeeeeeee eeee eeee eeee eeeeeeeee/eeeeeeee eeeeee (88 888:8 eee 888 888:8) ee eeee eeeeee. Me eee eeee ee eeeeeeeeeee, eeeeeeee ‌88‌ eeeeeeee eeee eeeeeeeeeee eeeeee eee eeeeeeee, eee eeeeeeeeeee ee eeeeeeee ee 88% eeeee. M eeeeeeeee-eeee eeeeeee eeeeeeee eeeeee eee eee eeeeeeeeeeeee ee eeeeeeee eeee eeeeeeeee M=M eeeee eee eeee eeee eeeeeeeee.[‌88‌] Meeeeeee eeeeeeeee(MM) eeeeeee ‌88‌ ee eeee ee eeeeee e eeeeee ee eeeeeeeee ee eeeeeeee ee eee eeeeeee, eee eee eeeeeeee ee eeeee ee eeeeee ee eeeeeeee eeeeee eeeeeeeee.

Mee eeeeeeeee-eeeeeeeee eeeeeeeeee eeeeeeeeeeeee ee α-eeeeeeee eeeeeee eeeeeeeee ee eeeeeee eeeeeee eeeeeeeeee eee eeee eeeeeeee eeeeeeeeeeeee ee eee eeeeee ee Meee[‌88‌] eee Meee[‌88‌] (‌Meeeee 88‌). Me eeee eeeee, e eeeeeeeee eeeeeeeee ee eeeeeeee eeee e eeeeee eeeeeeeeeeee eee e eeeeee eeeeeee eeeeee eeeeeeeee ee eee eeeeeeeeee eeee ee Meeeee.[‌88‌] Meeeeee ‌88‌ eeeeeeeeeee eeeeeeeeeeee eee ee eee eee eeeeeeeeeee ee 8-eeeeeeeeeeeeee ee eeeeee-8-ee eeee e eeeeeeeee/eeeeeeee eeeee ee 8888:8 ee eeee eeeeeeeeeee; eee eeeeeeeeeeeee eeeeeee ‌88‌ (M8 = Me; M8 = Me) ee eeeeeeee ee eeeeeeeeeeee eeeee eeee 88% ee. Me eeeee eeee eeeeeeeee-eeeee eeeeeeee, eeeee ee eeeeeeee eeee eee eeeeeeee(eeeeeee)eeeeeeeee(MM) eeeee, e eeeeee eeeeeeeeeeeee eeeeeeeeeeee, eee e eeeeee eeeeeee, e eeeee ee α-eeee eeeeeeeee eee eeeeeeeeeeeeeeeeee eeeeeee eeee ee ee 88% ee. Me eeeee 8.8 eee% ee eeeeeeee ‌88‌, eeeee eeeee (M)-eeeee-MMMMM {8,8′-eee[eee(8,8-eeeeeeeeeeeeee)eeeeeeeee]-8,8′-eeeeeeeeee} eee MMMM (8,8-eeeeeeeeeeeeee-8,8-eeeeeee) eeeeeee, eeeeeee α-eeee eeeeeeeee eee eeeeeeeeeeeeeeeeee eeeeeeeeeeee ee α-eeee eeeeeeee eeee ee ee 88% ee.[‌88‌]

‌Meeeee 88‌ Meeeeeeeee Meeeeeeeeeeee ee Meeeeee α-Meee Meeeeeeee Meeee Meeeeeeee Meeeeeeee[‌88‌,‌88‌]

‌Meeeeeeeeee 88‌

e Meeeeeeeee ee eeeeee-eeeee MM ee MMMM.

Meeeeeeeeeee Meeeeeeee

Meeeeeee ‌88‌ eee ‌88‌; Meeeeee Meeeeeeee Meeee Meeeeee ‌88‌:[‌88‌]

M eeeeeee ee {Me(Me*)Me8}8 (8 ee, 8.888 eeee, 8.8 eee% Me) eee M-(8-eeeeeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeeeeeeeee (8 ee, 8.888 eeee) eee eeeeeee ee eeeeeeeee M8M (88 eM) ee 88 °M eee 8 e, eeeeeeeeee eeeeeee ‌88‌. Mee eeeeeeeee eeeeeee eee eeeeeeeeeee ee ee eeeeeeeee eeeeeeee eeee e eeeee eeeee eeeeeeeeee e eeeeeee. Meeee eeeeee 8 M ee MMM (8–88 eeeee eeeeeeee ee eee eeeeeeee) eee eee eeeeeeee [88 eeee; eeeee (eeeeeeeee/eeeeeeee) 8888:8], eee eeeeeeeee eee eeeeeeee eeee M8 (8 ×) eee eeee eeeeee ee 88 °M eeee eeeeeeee eeeee M8 eeeeeeee (88 eee). Meeee eeeeeee ee ee eee eeeeeeeee eeeeeeeee M8, eee eeeeeee eee eeeeeeeee eeee Me8M (8 × 8 eM) eee eeeeee eeeeeee e eeeee eeeeee eee eeeeee, eeeeee MM eeeeeeee. Mee eeeeeeeee ee eee eeeeeee, eee eeeeeeee eeeeeee eeeee eee eeeee (Me8MM8), eeeeeeeeeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee).

Meeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Mee eeeeeeee (8.8–8 eee), eeeeeee (8 ee eeeee), eeeeeeeeee eeee eeeeeeeeee, eee eeeeeeee ‌88‌, ‌88‌, ee ‌88‌ eeee eeeeee eeeeeeee ee ee eeeeeeeee eeeeeeee eeee e eeeeeeeeee eeeeeeee eeeeee, eeeeeeee eee eeeeeeee eeeeeeeeeee eeeeeee, eee e eeeeeee/eeeeeee eeeeee eee eeeeeeee eeeeeeeeeee eeeeeeeeee. Mee eeeeee eeeeeeeee eee eeee eeeeee eeee M8 (8 × 8 eee) eee M8 (8 × 8 eee) eeeee eeeeeeee, eeeeee ee eee eeeeeeeeeee ee eee eeeeeeee M8 eeeeeeee. M M8 eeee eeeeeeee eeee e eeeeeeee eeeeeeeee, eee eeee ee eeeeeeee eeeeeeee eeeeee ee eeeeee eee eeeeeeeee eee eeeeeeeeeee ee M8, eee eeee. Mee eeeeeee eee eeee eeeeee ee eee eeeeeeee eeeeeeeeeee, eee eee M8 eeeeeeee ee eee eeeeeeeee eee eeeeeeeeee ee eee eeeeeee eeeee eeeeeeeeee eee eeeeeeee. Meee eeeeeeeeee ee eee eeeeeeee, eee eeeeeeeee eee eeeeee ee 88 °M. Me eee eeee eeeeeeeeeeeee eee eeeeee eeee M8 (8 × 8 eee). Mee eeeeeee eee eeeeeeeeeee ee e eeeee-eeeeeeee eeeee, eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeee eeeeeeeee ee eeeeeeeee eee eeeeeeee ee eeeeeeee eeeeee eeeeee eee eeeeeeee, eee eee eeeee eee eeeeeeeeee ee eee eeeee ee eee MM eeeeee ee eee eeeeeeeee eeeeeee.

Meeeeeee ‌88‌; Meeeeee Meeeeeeee Meeee Meeeeeee ‌88‌:[‌88‌]

Meeeeeee eeeeeeeeeee: Mee eeeeeeeeeeee eeeeee (8.888 eeee) eee {MeMe8(η8-eeeeeee)}8 (88 ee, 8.88 eeee) eeee eeeeeeeee ee eeeee eee eeeeeeee MMM (8 eM) eeeee e M8 eeeeeeeeee. Mee eeeeeee eee eeeeee ee 888–888 °M eee 8–8 e, eee eeee e eeee ee eee 8,8-eeeeeee (8.888 eeee) ee MMM (8 eM) eee eeeee, eee eee eeeeeee eee eeeeee ee ee eeeee eeeeeeee eeeeeeeee. Mee eeeeeee eee eeeeeee eeeee eeee eeeeee ee 88 °M, eee eee eeeeeee eee eeeee ee ee ee eeee eeeeeeee ‌88‌ ee ee eeeeee ee eee eeeee eeeee. Meeeeeee ‌88‌ eee eeee eeeeeeee ee eee eeeeeeeee eeeeeeee eeeeeee eeeeeee eeeeeeeeeeee.

Meeeeeeee eeeeeeeee: Meeeeeee ‌88‌ (8.888 eeee) eee eeeeee ee e 88-eM eeeeeeeeeeeee eeeeee. Meeee eMeMM (8.8 eM) eee eeeeeeeeee eeeee e eeeeeee, eee eee eeeeee eee eeeeee eeee M8 eee eeeeeeeeeee ee 88 eee. Meeee eee eeeeeeee eee eeeeeeee, eee α-eeee eeeeeeee (8 eeee) eee e 8.8 M eeee ee e-MeMM ee eMeMM (8.8 eM, 8.8 eeee) eeee eeeee. Mee eeeeee eee eeeeee eeee M8 eee eeeeeeeeeee ee 88 eee. Meeee eeeeeeee ee ee eee 8 e, eee eeeeeeee eee eeeeeee. Mee eeeeeee eee eeeeeeee eeeeeee e eeeee eeeeee eee eeeeee, eee eee eeeeeeee eee eeeeeee eeee eeeeeee eee eeeeeeee ee MM ee eeeeeeeee eee eeeeeeeeee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MM ee MMMM eeeee eeeee eeeeeeeeeeeeee (eeeeee eee).

References