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2.13.2.3.1 Reactions Catalyzed by Chiral Lanthanum Complexes

DOI: 10.1055/sos-SD-202-00331

Yliniemelä-Sipari, S. M.; Pihko, P. M.Science of Synthesis: Stereoselective Synthesis, (20112662.

Shibasakiʼs first-generation catalyst (S)-22 [(S)-LLB] was the first catalyst within the category of bifunctional multimetallic asymmetric catalysis that was shown to promote nitroaldol reactions of unmodified nitroalkanes with a variety of aldehydes with good yields and enantioselectivities (Scheme 44).[‌178‌] Preparation of the catalyst 22 can be performed by treatment of lanthanum(III) isopropoxide with the lithium salt of 1,1-binaphthalene-2,2-diol (BINOL) in the presence of a small amount of water, although equally active catalyst can be prepared by several alternative procedures.[‌179‌,‌180‌] The complex maintains its activity for several months if stored under argon at ambient temperature, and special precautions for its handling are not necessary. The nitroaldol reaction using the first-generation catalyst (R)-22 [(R)-LLB] has been successfully used as key step in the synthesis of β-blockers[‌179‌,‌181‌,‌182‌] and allo-phenylnorstatine.[‌183‌]

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M8 ee (%) Meeee (%) Mee
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M8 M8 M ee (eee/eeee) ee (%) (eee) Meeee (%) Mee
(MM8)8Me Me M 88:88 88 88 [‌888‌]
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M8 M8 Meeeeeee Meee (e) Meee (°M) ee (eee/eeee) ee (%) ee eee Meeee (%) Mee
Me M 88 88 88 88 8.8 [‌888‌]
Me M 88/MeMe/M8M 88 88 88 88 [‌888‌]
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References


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