Enantioselective Synthesis of P‐Stereogenic Alkynylphosphine Oxides by Rh‐Catalyzed [2+2+2] Cycloaddition

Abstract

Drei mal zwei: Eine enantioselektive Synthese von P‐stereogenen Alkinylphosphinoxiden verläuft über eine [2+2+2]‐Cycloaddition symmetrischer Dialkinylphosphinoxide mit 1,6‐Diinen (siehe Schema; Z=CH2, O oder N‐Sulfonamid), wobei kationische Rhodium(I)‐Komplexe von modifizierten Binap‐Liganden als Katalysatoren wirken. Mit der Methode sind auch C2‐symmetrische P‐stereogene Bis(alkinylphosphinoxide) zugänglich.

Transition‐Metal‐Catalyzed Enantioselective [2+2+2] Cycloadditions for the Synthesis of Axially Chiral Biaryls

“…28–32 Thus, our research group investigated the use of alkynylphosphonates or phosphine oxides instead of alkynyl carbonyl compounds for the practical synthesis of axially chiral biaryl phosphorus compounds 32. 34, 35 Pleasingly, enantioselective [2+2+2] cycloadditons of 2‐naphthol‐derived alkynylphosphonates or phosphine oxides 48 with symmetrical 1,6‐diynes 45 in the presence of the catioinc rhodium(I)/H 8 ‐binap catalyst furnished axially chiral biaryl phosphorus compounds 49 in high yields with high enantioselectivity (Scheme ) 34. Furthermore, the catalytic activity of this rhodium catalyst is very high so that the reaction could be completed even with 1 mol % of the catalyst.…”

Efficient Synthesis of P-Chirogenic Compounds Enabled by Chiral Selenide-Catalyzed Enantioselective Electrophilic Aromatic Halogenation

“…To avoid the consumption of stoichiometric amounts of chiral reagents, asymmetric catalytic methods such as metal-catalyzed asymmetric couplings [12][13][14][15][16][17][18][19][20] and desymmetrization of prochiral phosphorus molecules have been developed. [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] Particularly, desymmetrization methods have been a more focus lately. Typical examples include transition metalcatalyzed intra-and intermolecular C-H functionalization, [22][23][24][25][26][27][28] Mo-and Ru-catalyzed ring-closing metathesis, 29,30 Rh-catalyzed cycloaddition and hydroarylation, 31,32 Au-catalyzed intramolecular hydroetherification, 33 Nheterocyclic carbene (NHC)-catalyzed esterification, 34 Tm-catalyzed intermolecular sulfenylation, 35 and cinchona alkaloid-catalyzed allylic alkylation reaction.…”

Asymmetric Vinylogous Aldol-type Reactions of Aldehydes with Allyl Phosphonate and Sulfone

“…In such reactions, synthetically versatile chiral vinylogous products containing α,β-unsaturated phosphonate or phosphine oxide moiety or α,β-unsaturated sulfone motif (Nishida et al., 2008, Xue et al., 2011, Konno et al., 2012, Lefevre et al., 2013, Hornillos et al., 2015, Lim and Hayashi, 2015, Lim and Hayashi, 2017, Wang and Hayashi, 2018, El-Awa et al., 2009, Alba et al., 2010, Nielsen et al., 2010, Zhu and Lu, 2010, Moteki et al., 2010, Quintard et al., 2011, Moure et al., 2011, Nishimura et al., 2012, Halskov et al., 2012, Zhou et al., 2012, Hernández-Toribio et al., 2012), would be produced. Furthermore, phosphonates and phosphine oxides had great applications in medicinal and agricultural chemistry (Mucha et al., 2011, Ordóñez et al., 2012, Corbridge, 2013, Horsman and Zechel, 2017).…”