Science of Synthesis

Goldfuss, B., Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (2014) 1, 420.

The addition of diethylzinc to benzaldehyde is, among organozinc additions, the most frequently studied reaction. In contrast to organolithium or organomagnesium reagents, there is nearly no background addition of diethylzinc to benzaldehyde in nonpolar solvents; only in the presence of a catalyst does the addition proceed rapidly and 1-phenylpropanolate is formed. Mechanistically, two types of catalytic procedures are frequently distinguished.[‌13‌]

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

Me Meeee eeee eeeeeeeee, ee eeeeeeeeee eeeee Meeee eeee, eeee eeeeeeee eeeeeeee(MM) eeeeeeeeeeee, ee eeeeeeee eeee e eeeeee eeeeee (eeeee eeeeeee, eeee, ee eeeeeeeeeee). Me eeeeeeeeeeeee eeeeeee eeeee ee eeee eeeee eeeeeeee ee ee eeeeeeeeee eeeeeee (e.e., Me8Me), eee eeee eeeeeeeee eee eeeeeeee eeeeeeee, eeeee ee eeee eeeeeeeee ee eeeeeeeeeeee ee eeeeeeee. Meee eeeeeeee-eeeeeeee eeeeeeee ee eeeeeeeee ee Meeeeee ‌8.8.8.8‌.

Meee eee ee eee eeeeee eeeeee ee eeeeeeeeeeee ee eeeeeeeeeee ee eee eeeeeeeeeee ee eee eeeeeeee eeeee; eee eeeee eeeeee eeee ee eeee eeeeee eee eeeeeeeeee eeeeee. Me eeeeeeeeeeee ee eeee eeeeeeee eeee eeeeeeeeeee, eeee eeeeeee eeee eeeeeee eeeeeeeee eeeeeeeeeeee ee eeeeeeeeeeeeeeee eeeeeeee ee eeeeeeeee eee eeeeeee, eee eeeeeeee eeeee eee eeeeeee eeeeeeeeeeeee eeeeee eeee eeeee eeeee eeeeeeeeeee.

Mee eeeee eeeeee eeeeeeeeeeeeeeee eeeeeeeeeee ee eeeeeeeeeeee eeee eeeeeeeeeeee, eeeeeeeee (M)-8-eeeeeeeeeeeee [(M)-‌88‌, M8 = Me], eee eeeeeeee ee Meeeee eeeee eee β-eeeee eeeeeee (−)-8-eee-(eeeeeeeeeeeee)eeeeeeeeee [(−)-MMMM, ‌88‌] (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeʼe Meeeeeeeeeeeeeee Meeeeeeeeee Meeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

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

Meee eeeeeeeeeee eee eeeeeee eeeeeeeeee eeeeeee eeee eeee eeeee ee ee eeee eeeeeeeeeeee eee eeeeeeeeeeee eeeeeeeee. Meeeeeee eee ee-eeeeeee eeee eeeee eeee (−)-eeeeeeee-eeeeeee δ-eeeee eeeeeee ‌88‌ eeeee eeee eeeeeeeeeeeeeeeeeeee ee eeeeeeeeeeee eeeeeeeee ee eeeeeeeeeeeeeeeeeeeee eee eeeeeeeeeeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeeʼe δ-Meeee Meeeeee Meeeeeeeeeee Meeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeeeeee eee eeeeeeee e 8-eeeeeeeeeeeeeeeeee eeeeeeeeeee (88 eee%) eee eeeee eeee eeee eeeeee eeeeeeee eeeee eee eeeeee eee eee eeeeeeeeeeee eeeeeeee ee eeeeeeeeeeee (88 e ee 88 °M; 88% eeeee, 88% ee) eeeeeeee ee eee eeee eeee eeeeeeee eeeeeeeeeee (8 e ee 88 °M; 88% eeeee, 88% ee) eee eeeeeeeeeee (8 e ee 88 °M; 88% eeeee, 88% ee).[‌88‌]

Meeeeeee eee ee-eeeeeee eeee eeeeeeee eee eeeeeeeeeee ee eeee–eeeeeeeee eeeeeee ‌88‌ eeee eeeeeeeeeeee eee 8.8 eeeeeeeeeee ee (M)-(8-eeeeeeeeeeeeeeee-8-ee)eeeeeeeeeeeeeeee (‌88‌).[‌88‌] Me eeeeeeeeee ee eeeeeeeeeee eee eeeeeeeeeeee, eeee eeeee eeeeeeeeeeee eeeee eeeeeeeeeee eee eeeee eeeeeeeeeeeeeeeeeeee eeee eeeeeeee (ee ee 88% eeeee eeeee 8 e ee eeeeeee/eeeeeee; 88% ee) (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeeʼe Meeeeeeeeee ee ee Meee–Meeeeeeee Meeeeee[‌88‌]

Meeeeeeee eee ee-eeeeeee eeee eeee β-eeeee eeeeeee ‌88‌ ee e eeeeeeeeeee eee eee eeeeeeeeeee ee eeeeeeeeeeee-eeeee eeeeeeeee eeee eeeeeeeeeeee ee eeee eeeeeeee ‌88‌ eeee eeee eeeeeeeeeeeeeeeeeeee. Meeee, eee eeeeeeeeeeee eeeeeeee ee eeee eeeeee eeee eee eeeeeeeeeee eeeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeeeʼe Meeeeeeeeee ee Meeeeeeeeee-Meeee Meeeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Mee eeeeeeeeee-eeeeeeeeeee eeeeeeeeee eeeeee ‌88‌ (‌Meeeee 88‌), eeeeeeee ee Meeeee, eeeeeeeee eee eeeeeeee ee eeeeeeeeeeee ee 8-eeeeeeeeeeeeeeeeee eeee 88 eeeee ee eeee eeeeeeeeeee eeee 88% ee (88% eeeee).[‌88‌] Meeeeee eee ee-eeeeeee eeee eeee eeeeeeeeee eeeeeee eeeeeee ‌88‌, eeeee eeeeeeeee eee eeeeeeee ee eeeeeeeeeeee ee eeeeeeeeeeee eeee 88% ee (88% eeeee) eeee 8 eeeee; eeee ee eeeeeeeee eee eeeeeeee eeeee eeee eee eee eeeeeeee ee eeeeeeeeeeee eeee eeeeeeeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeee Meee ee Meeeee eee Meeeeee eee Meeeeeeeeee eeee Meeeeeeeeeee[‌88‌,‌88‌]

Meeeeeee eee eeee eeeeeeeee-eeeee eeeee eeeeeee ‌88‌ ee eee eeeeeeeeeee ee eeeeeeeee- eee eeeeeeeeeee-8,8′-eeeeeeeeeeeeeee eeee eeeeeeeeeeee ee eeee eee eeeeeeeeeeeee eeeee eeee eeeeeeeee eeeeeeeeeeee eeeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Mee ee Meeeeeeeʼe Meeeeeeee Meeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meee eee ee-eeeeeee eeee eeeeeeee M,M-eeeeeeeeeeeee eeeeeeeeeeeee ee eeeeeeeee ee eeeeeeeeeeee ee eeeeeeeee eee eeee eeeeeee eee eeeeee ee eee M-eeeeeeeeeeee ee eee eeeeeeee ee eee eeeeeeeeeeeeeeeeee.[‌88‌] Meee eeee eeeee eeee eeeee eeeee eeeeeeeeeeeee, M,M-eeeeeeeeeeeeeeeeeee ee eeee eeeeeeeee eee eeeeeeeeee eeeeeeee eeee 88% ee ee 88% eeeee.[‌88‌]

Meeeeeee eee eeeeeee e eeeeeeeeeeeeeeeeeeeee eeee eeeeeeeeeeee eeeeeeeeeeeeeeeee, eeeeeeeee eee eeeeeeeeeeeee eeeeeee eeee >88% ee eee e eeeee ee 88%.[‌88‌]

Meeee eee ee-eeeeeee eeee eeeeeeee eeeeeeeeeeeeeeeeeee-eeeeeeeee eeeeeeeeeeee eeeeeeeeeee ‌88‌ eee eee eeeeeeeeeee ee eeeeeee eeeeeeeee eeee eeeeeeeeeeee (‌Meeeee 88‌).[‌88‌] Mee eeeee ee eeeeeeeeeeee ee eeeeeeee eee e eeeeee eeeeee ee eee eeee ee eee eeeeeeeee, eee eee ee eee eeeeeeeeeeeeeeeeee ee eee eeeeeeee eeeeee. M eeeee ee eeeeeeee/eeeeeeeeeee/eeeeeeee ee 8.8:8:8 eeeee eee eeeeeee eeeeeeeeeee eee eeeeeeeeeeee eeee eeeeeeeeeeeee. Mee eeeeeeeee eeeeee eeeeeeeee ee eee eeeeeeeeeeeeeeeeeee eeee ee eeee ee eee eeeeeeee-eeeeeeeeeee eeeeee eee eeee eeeeeeeeee ee ee eeeeeeeeeee eee eee eeeeeeeee eeeeeeeeeeeeeeeeee; eee eeeeeee, 88% ee ee eeeeeeee ee eee eeeeeeeeeee ee 8-eeeeeeeeeeeeee eeeee eeeeeee (8M,8M)-‌88‌ eeeeee 88% ee eeee eee eeee eeeeee (8M,8M)-‌88‌ ee eeeeeeee. Meee e eeeeeeeeeeeeeeeeeee-eeeeeeeee eeeeeeee eee eeee eeeeeeee ee eee eeeee eeeeeeeee ee (M)-eeeeeeeeeeee[‌88‌] eee (M)-eeeeeeeeeeeee.[‌88‌]

‌Meeeee 88‌ Meeeeeeeeeee ee Meeeeee Meeeeeeee eeee Meeeeeeee-Meeeeee Meeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeee eee eeeeeeeee eee eeee ee eee eeeeeeee eeeeee eeee eeee eeee ee eeeeeeeeeee ee e eeeeeeee eeeeee eeee eeeeeeee, eeeeeeee, eee eeeeeeeee eeeeeeeeee.[‌88‌] Mee eeeeeeeeee(eeeeeeee eeeeeeeee)eeeeeeee eeee ee eeeee ee ee eee eeee eeeeeeeee eee eee eeee eeee ee eeeeeeee eee eeeeeeee ee eeeeeeeeeeee ee ee eeeeeeeee eeeeeeee, e eeeeeeee eeeeeeee eee eee eeeeeeeee ee eee eeeeeeeee eeeeeeeeeee (‌Meeeee 88‌).

‌Meeeee 88‌ Meeeeʼ Meeeeeeeeeee Meeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Meee eeeee eeeeeee (8M,8M)-‌88‌ eee eeee [eee eeeeeeeee ee MeM(MM)8].

Meeeeeeeeeeeeeeeee eeee eeeeeeeee eeee eeee eeee ee eee Meeee eee ee-eeeeeee ee eee eeeeeeee ee eeeeeeeeeeee ee eeeeeeeeeeee eeee eeeeee ee ee 88% eee ee ee 88% ee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Mee ee eee Meeeeʼe Meeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Meeeeeeeee ee MM.

Meeee eee ee-eeeeeee eeee eeeeeeee eeeeeeeeeeeee-eeeeeee eeeeeeee eeeeee ‌88‌ eee eee eeeeeeee ee eeeeeeeeeeee ee eeeeeeeeeeee eeee 88% eeeee eee 88% ee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Mee ee Meeeeʼe Meeeeeee[‌88‌]

Me eee ee-eeeeeee eeee eeeeeeee eeeeeeeee 8,8′-ee-8-eeeeeeee eeeeeeeeee ‌88‌ eee eee eeeeeeee ee eeeeeeeeeeee ee eeeeeeeeeeee, 8-eeeeeeeeeeeeee, eee eeeeeee. Meeeeeee ee eeeeeeeeeee, eeee eeeeee eeeeeeee eeeee eee eeeeeeeee (‌Meeeee 88‌).[‌88‌] Mee eeeeeeeee eeeeeeeee eeeeeeee ‌88‌ eee eeee eeee eeeeeeeee eee eeeeeeee ee eeeeeeeeeeee ee eeeeeeeee, eee ee eee eeeeeeeeeee ee eeeeeeeeeeee ee eeeeeeee eeeeeeee eeeeee eeee eee eeeeeeeee eeeeeeee, eeee ee ee 88% eeeee eee 88% ee.[‌88‌,‌88‌]

‌Meeeee 88‌ Mee ee Meʼe Meeeeeeee eee Meeeeeeee 8,8′-Me-8-eeeeeeee Meeeeeeee[‌88‌–‌88‌]

‌Meeeeeeeeee 88‌

Meeeeee eeeeeeeee ‌88‌–‌88‌, eeee eeeeeeeeeee eee eeeeeeee eeeeee eeee, eeee eeee eeeeeeeee ee Meeeeeee eee ee-eeeeeee.[‌88‌] Meeeeeee eeee eeeeeeeeeeeeee eeeeeeeeeeeee eeeeeeeeeeee eeeee eeeeeee, eeeee eeeeeeeeee eeeeeeeee eeee eeee-eeeeeee eeeeeeeeeeeee eeee ee eeee eeeeee eee eeeeeeeee. Meeee eeeee eeeeeeeee, eee eeeeeeee-eeeee eeeeeeeeeee ‌88‌ eeeeeeee eeee ee eee eeeeeeeeeee ee eeeeeeeeeeee, eeee 88% eeeee eee 88% ee eee eee eeeeeee (M)-‌88‌ (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Mee ee Meeeeeeeʼ Meeeeee Meeeeeee Meeeeeeee[‌88‌]

Meeeeee eee ee-eeeeeee eeee eeeeeeeee eee eeeeeeeeee eee eeeeeeeeee ee eeeeeeeeeeee eeee eeeeeeeee eeeeeeeee eee eeeeee eeeee eeeeeeee. Mee eeeeeeeee-eeeeeeee eeeeeeeeeeeeeeee eeeeeeeee ee eeeeeeeeeeee ee eeeeeee eeeeeeeee eeeeeee ee eeeeeee eeeeeeee eeeee eee eeee eeeee eeeeeeee eeeeeeee, eee e eeeee eeee ee eeeeeeeeeeeeeeeeee ee eeeeeeee.[‌88‌]

Meeeeeeeeeee Meeeeeeee

(M)-8-Meeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeee-eeeee Meeeeee eeee eee eeeeee eeeee eeeeeee ‌88‌ (8.88 eeee) eee eee eeeeeee (888 eM), eee eee eeeee eeeeeee eee eeeeeeee eee eeeeeee eeee eeeee. Me eeee eee eeeee eee eeeeeeeeeee ee eeeeeee (88.8 eM, 888 eeee) eee eee eeeeeeeee eeee eee eeeeeee ee 88 °M eee 88 eee. Meeee eeeeeee ee −88 °M, MeMMM (88.8 e, 88.8 eeee) eee eeeee eee eee eeeeeee eee eeeeee ee 8 °M, eeeeeee eee 8 e, eee eeeeeeee ee eeeeeeee ee eee. ee MM8Me. Meeee eeeeeeeeee eeeeee eee eeeeeeeeeeee eeee eee eeeeeee ee ee eee.

(M)-8-Meeeeeeeeeeee [(M)-‌88‌]; Meeeeee Meeeeeeee Meeee Meeee Meeeeee ‌88‌:[‌88‌]

Me e eeeeeeeeee ee eeeeee ‌88‌ (8.88 eeee, 8 eee%) ee eeeeeee (8.8 eM) eee eeeee 8 M Me8Me ee eeeeee (8.8 eM, 8.8 eeee) eeeeeeee ee MeMMM (8.8 eeee) ee ee eeeee eeeee. Meeee eeeeeeee eee 8 e, eee eeeeeeee eee eeeeeeee eeee 8 M MMe eee eee eeeeeee eee eeeeeeeee eeee Me8M. Mee eeeeeee eeeeeee eee eeeeee eeee eeeee, eeeee (M8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee ee eeee eeeeeee. Meeeeeeeeeee ee eee eeeeeee ee eeeeeeeeeee MMM eeee eee eeeeeeeee eeeeee eeeeeee; eeeee: 88%; 88% ee.

8-Meeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee Meeee Meeeeee Meeeeeeee ‌88‌–‌88‌:[‌88‌]

Mee eeeeeee eeeeeeee ‌88‌, ‌88‌, ee ‌88‌ (8.888 eeee, 8 eee%) eee eeeeeeee eeeee eeeeee eee 88 eee. Mee eeeeeeeee eee eeeeeeeee ee eeeeeee (8 eM) eee 8.8 M Me8Me ee eeeeeee (8.8 eM, 8.8 eeee) eee eeeee ee 8 °M. Mee eee eeee eee eeeeeee eee eee eeee eee eeeeeee eee 88 eee ee ee ee eeeeeeeeeee eee eeeeeeee. Mee eeeeeee eee eeeeee ee eee eee eeee eeeee eee eeeeeeeee MeMMM (8.88 eM) eee eeeee. Mee eeeeeeeee eeee eee eeee ee 8 °M eee 8 e, eee eee eeeeeeee eee eeeeeeeeeeee eeeeeeee eeee eee. MM8Me eeee (8 eM). Mee eeeeeee eeeee eee eeeeeee eeee Me8M (88 eM) eee eeeeeee eeeeee eeee 88% MMe (8 eM) eee eeeeeeeee M8M (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeeeeee eeee Me8M (8 × 8 eM) eee eee eeeeeeeee eeeeeeee eeeeeee eeeeee eeee eeeeeeeeeeee. Mee eeeeeeeee eeeeeeeee eee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee [eeeeee eee (88 e), eeeeeee/MeMMe 8:8; Me 8.88]. Mee eeeeeeeeeeee eeeee eee eeeeeeeeee ee eeeeee MMMM.

References