Science of Synthesis

MacMillan, D. W. C.; Watson, A. J. B., Science of Synthesis: Asymmetric Organocatalysis, (2012) 1, 379.

Chiral phosphines and derivatives are highly valued and extensively utilized as ligands for various metals within asymmetric catalysis[‌168‌–‌171‌] and are also found within a selection of biologically relevant materials.[‌172‌] Preparation of these synthetically important compounds generally revolves around the use of chiral auxiliaries or resolution-based techniques.[‌168‌–‌171‌,‌173‌] However, following the success of iminium catalysis as a general method for the introduction of stereogenic heteroatom functionality, extension to phosphorus-based nucleophiles has enabled the realization of a catalytic asymmetric synthesis of chiral phosphine products and analogues thereof.[‌174‌]

Mee 8,8-eeeeeeee ee eeeeeeeeee eeeeeeeeeeee (ee eeeeeee-Meeeeee eeeeeeee) eee eeee eee eeeeeee ee eeee eeeeeeee eee e eeeeee ee eeeeeeeeeeee eeee eeeeeee eeee eeeee eeeeeee.[‌888‌] Meeeeee, eeeeeeeee eeeeeeee ee eeeee eeee eeee eeeeeeee, eeeeee eeeeeeeeeee 8,8-eeeeeeee eee eee eeeeeeeeeeeee ee eee eeeeeee 8,8-eeeeeeee eeeeeee. Meeeeee eeee, eeeeeeeeee eeeeeee-eeeeeeeee eeeeeeeeeeeeeeeeee eee eeeeeeee ee eeeeeee eeeeeeeeeeee eeeeee eeeeeeeeeeeeee, eeeeeee ee ee eeeeeeeee eeeeee eee eee eeeeeeeee ee eeeeeeeeeeeeeee eeeeeeeeee-eeeeeeeeee eeeeeeeee.[‌888‌,‌888‌,‌888‌–‌888‌]

Mee eeeeeeeee eeeee ee eeeeeeeeee eeee eeeeeeeeeeeeee ee eeeeee eeeeeeeeee eeeeee eeeeeeeee eeeeeee, eeeeeeeeeeeeee eeeeee eee eeeeeeeee, eeeeee, eeeeee, eee eeeeeee. Mee eeeeeeeeeeee eeeeeeeeee eee eeeeeeeeee ee eeeeeeeeee, eee eee eeeeeeeeeeeee eeeeeeee eee eeeeeeeee eeeeeeee ee eeeeee eee eeeeeeeee–eeeeee eeeeeee ‌88‌ (eeeeeeeee eeeeeeeeeeee), ee eee eeeeeeeee eeeee ee eeeeeeeeeee ‌88‌ (eeeeeeeee eeeeeeeeeeee eee eeeeeeeee eeeeeeeeeeee, eeeeeeeeeeee). Meeeee eeeee eeee eeeeeeee ee eeeeeeeee eeee eeeeeeeeeeeeeeeeeeee eeeeeeeee eeeeeeeee (‌Meeeee 88‌). Meeeeeeeee eee eeee eeeeeee, eeee eee eeeeeeeeee eeeeeeeeeee eeeee ee e eeeeeee ee eeeeeeee eee eeeeeeeee. Mee eeeeeeeee eeeeeeeeeeee, eeeeeeeee ee eee ee eeeeeeee, eeeeeeeeee ee eeeee eeeeeeee eeeeeeeee ee eee eeeeeeeeeee eee eeeeeee; eee eeeeee eee eeeeeeeeeeee ee eeeeeeeeeee, ee ee eee eeeeeeeee ee eeeee ‌88‌ (‌Meeeee 88‌).

‌Meeeee 88‌ Meeeeeeeeeeeeeee 8,8-Meeeeeee ee Meeeeeeeee Meeeeeeeeeee[‌888‌,‌888‌–‌888‌]

‌Meeeeeeeeee 88‌

e Meeee ee eeeeeeee eeeeeeee ‌88‌, eeeeeeee ee ee eeee eeeeeeeee ee eee eeeeeeeeeeee eeeeeeeee eeeeeeee eeee M8 (ee MeMM8 eeeeeeeee).

e ee ee eeeeeee ‌88‌, eeeeeeee ee ee eeee eeeeeeeee ee eee eeeeeeeeeeee eeeeeeeee eeeeeeee eeee MeMM8 (ee M8 eeeeeeeee).

‌Meeeee 88‌ Meeeeeeee ee Meeeeee eee Meeeeeeeeeeeee eee Meeeeeeeeeeee ee Meeeeeeeeeee Meeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

(M)-8-(Meeeeeeeeeeeeeeee)-8-(8-eeeee)eeeeee-8-ee–Meeeee Meeeeee (‌88‌, M8 = 8-Meeee; M8 = Me; M8 = M); Meeeeee Meeeeeeee:[‌888‌]

Mee eeeeeeee eee eeeeeee eee eeeee eeeee-eeeee eeeeeeeee eee eeeee ee eeeee eeeeeeeeee. Me (M)-8-{eee[8,8-eee(eeeeeeeeeeeeeee)eeeeee](eeeeeeeeeeeeeee)eeeeee}eeeeeeeeeee (‌88‌; 88 ee, 8.88 eeee, 8.8 eeeee) ee Me8M (8.8 eM) ee ee eee eeeee (M)-8-(8-eeeee)eeeeeeee (88 ee, 8.8 eeee, 8.8 eeeee). Mee eeeeeee eee eeeeeee ee ee eee 8 eee eeeeee eeeee eeeeee ee −88 °M eee eeeeeee eee 88 eee eeeeee eeeeeeee ee Me8MM (88 ee, 8.8 eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee eee 88 e eeeeee eeeee eeeeee ee −88 °M eee eeeeeee eeee MMM (8.8 eM). MeMM8 (88 ee, 8.8 eeee, 8.8 eeeee) eee eeee eeeee eee eee eeeeeee eee eeeeeee eee 88 eee eeeeee eeeeeeee ee e eeee ee MeMM (88 ee, 8.8 eeee, 8 eeeee) ee MMM (8.8 eM). Mee eeeeeeeee eeeeeee eee eeeeeee eee 88 eee eeeeee eeeee eeeeeeee eeee M8M (eeeeeee eeeee) eee eeee eeeeeee eeee eeeee (8 eM) eee eeeeeeeee eeee MeMMe (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (Me8M/MM8Me8 8:88); eeeee: 88.8 ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM-M eeeeee, eMeMM/eeeeee 8:8, 888/888 ee, 8.88 eM · eee−8; eM (eeeee) = 8.8 eee, eM (eeeee) = 8.8 eee].

Meeeeeeeeee (M)-(8-Meeeeeeee-8-ee)eeeeeeeeeee (‌88‌, M8 = Me; M8 = MeMe); Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeee ee (M)-8-{eee[8,8-eee(eeeeeeeeeeeeeee)eeeeee](eeeeeeeeeeeeeee)eeeeee}eeeeeeeeeee (‌88‌; 88 ee, 8.88 eeee, 8.8 eeeee), MeMM (88 ee, 8.8 eeee, 8 eeeee), eee (M)-eeee-8-eeee (88 ee, 8.8 eeee, 8 eeeee) ee MM8Me8 (8 eM) ee ee eee eeeee M(MeMe)8 (88 ee, 8.8 eeee, 8 eeeee) eee MeM (88 ee, 8.8 eeee, 8 eeeee). Mee eeeeeee eee eeeeeee ee ee eeeee eeeeeeeeeee ee eee eeeeeeeee eee eeee eeeeeeee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMM/Me8M 8:88); eeeee: 88 ee (88%). Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee eeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eee eeeeeeeeee eeee eee eeeeeeeeeeeee 8-eeeeeeeeeeee eeeee ‌88‌ ee eeeeeeeee eeeee.

(M)-8-(Meeeeeeeeeeeeeeeeeeeee)eeeeee 8-Meeeeeeeeeeee (‌88‌):[‌888‌]

Me eeeeeeeeeee (M)-(8-eeeeeeeee-8-ee)eeeeeeeeeee [‌88‌, M8 = Me; M8 = MeMe; 8 eeeee] ee MeMM (eeeeee eee eeeeeeee) eee eeeee MeMM8 (8 eeeee). Mee eeeeeee eee eeeeeee eee 8 e eeeeee eeeee eeeeeeee eeee M8M eee eeeeeeeee eeee MM8Me8. Mee eeeeeee eeeeeeee eeee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeeee ee MM8Me8. Meee eeeeeee eee eeeeeee eeee 8-eeeeeeeeeeee eeeeeeee (8.8 eeeee), MMMM (eeeeeeeee eeeeeeee), eee Me8M (8.8 eeeee) eee eeeeeee eee 8 e eeeeee eeeee eeeeee eeee 8 M ee MMe eee eee. ee MeMMM8. Mee eeeeeee eeeeeee eee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMM/MM8Me8 8:88); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM eeeeee, eMeMM/eeeeee 8:88, 8 eM · eee−8; eM (eeeee) = 88.8 eee, eM (eeeee) = 88.8 eee].

(M)-8-(Meeeeeeeeeeeeeeeee)-8-(8-eeeeeeeeeee)eeeeeeee (‌88‌, M8 = 8-M8MM8M8; M8 = Me); Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeee ee (M)-8-[eeeeeeee(eeeeeeeeeeeeeee)eeeeee]eeeeeeeeeee (‌88‌; 88.8 ee, 8.88 eeee, 8.8 eeeee) eee 8-MM8M8MM8M (8.8 ee, 8.888 eeee, 8.8 eeeee) ee MMMe8 (8 eM) ee 8 °M eee eeeee (M)-8-(8-eeeeeeeeeee)eeeeeeee (88.8 ee, 8.88 eeee, 8 eeeee). Mee eeeeeee eee eeeeeee eeee eeeee eeeeee eeeeeeee ee Me8MM (88.8 ee, 8.8 eeee, 8.8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 8 °M eee 88 eee eeeeee eeeeeeee ee M8 (88.8 ee, 8.888 eeee, 8.8 eeeee) ee M8M/eeeeeeee (8:88; 8.8 eM). Mee eeeeeeeee eeeeeee eee eeeeeee ee ee eee 8 eee eeeeee eeeee eeeeeeee eeeeeeee (ee eeeee eeeeee eeeeeee eeeeeeee) ee eeeee eeeeee eeeeeeeeeeeeee (eeeeeee eee eeeeeeee); eeeee: 88.8 ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee eeeeeeeee ee eee eeeee β-eeeeeeeeeeeeeeeee eeeeeeee ee eee eeeeeeeeeeeee eeeeeee ee eeeeeeeee ee eee eeeee eeeeeee eeee MeMM8 eee MeMM (eeeeeee eee eeeeeeee). Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM eeeeee, eMeMM/eeeeee 8:8, 888 ee, 8 eM · eee−8; eM (eeeee) = 88.8 eee, eM (eeeee) = 88.8 eee].

References