Acylsilanes as a new type of “hard” carbon prenucleophile reacted with monosubstituted allyl reagents under Pd-catalyzed asymmetric allylic alkylation reaction conditions to provide products with high regio-, diastereo-, and enantioselectivities. The usefulness of the protocol has been demonstrated by the ready conversion of the allylated products into the corresponding alcohols, esters, and ketones with retention of stereochemistry as well as by the enantioselective synthesis of cis-3-ethyl-4-phenylpiperidine and cinnamomumolide.

The BINOL−amino alcohol compound (S)-4 was found to conduct enantioselective fluorescent recognition of a serine derivative with an unprecedented high ef [enantioselective fluorescent enhancement = (ID − I0)/(IL − I0)] of 12.5. Both (S)-4 and (S)-5 are also found to be highly enantioselective fluorescent sensors for a number of other amino acid derivatives.

The asymmetric catalytic synthesis of β-substituted tryptophan derivatives was realized in high diastereo- and enantioselectivity by the reaction of glycine derivatives with sulfonylindoles in the presence of catalyst derived from AgCl and a commercially available chiral monodentate phosphoramidite ligand. The resulting adduct was readily converted to β-substituted tryptophan in 95% overall yield for two steps, which presented a highly efficient route to chiral β-substituted tryptophan.

The first highly diastereo- and enantioselective catalytic asymmetric Michael addition of glycine derivatives to nitroalkenes have been developed. The enantioselectivity of ortho-substituted products can be significantly improved by using a new 1,2-P,N-ferrocene ligand L5. The α,γ-diaminoacid derivative was obtained without the loss of optical activity from the adduct.

Regio- and enantio-selectivities in Pd-catalyzed allylic substitution reaction of monosubstituted allylic substrates with substituted benzyl alcohols were realized, affording the corresponding products in high regioselectivity (up to 93/7) and enantioselectivity (up to 96%).(R)-1-((1-Phenylallyloxy)methyl)benzeneC16H16O[α]D20=+15.0 (c 0.99, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-(1-(Benzyloxy)allyl)-4-methylbenzeneC17H18O[α]D20=+16.0 (c 1.14, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-((1-(4-Methoxyphenyl)allyloxy)methyl)benzeneC17H18O2[α]D20=+20.0 (c 2.19, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-(1-(Benzyloxy)allyl)naphthaleneC20H18O[α]D20=+30.2 (c 0.93, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-2-(1-(Benzyloxy)allyl)furanC14H14O2[α]D20=+31.1 (c 0.53, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-((1-(3-Methoxyphenyl)allyloxy)methyl)benzeneC17H18O2[α]D20=+16.4 (c 1.04, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-(1-(Benzyloxy)allyl)-4-fluorobenzeneC16H15FO[α]D20=+7.7 (c 1.05, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-(1-(Benzyloxy)allyl)-4-chlorobenzeneC16H15ClO[α]D20=+11.7 (c 1.32, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-(1-(Benzyloxy)allyl)-4-bromobenzeneC16H15BrO[α]D20=+11.7 (c 1.61, CH2Cl2)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-Methyl-4-((1-phenylallyloxy)methyl)benzeneC17H18O[α]D20=+13.0 (c 1.22, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-(1-(4-Methoxybenzyloxy)allyl)benzeneC17H18O2[α]D20=+14.9 (c 0.99, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-Fluoro-4-((1-phenylallyloxy)methyl)benzeneC16H15FO[α]D20=+8.0 (c 0.99, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-1-Chloro-4-((1-phenylallyloxy)methyl)benzeneC16H15ClO[α]D20=+9.2 (c 1.16, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)(R)-(3-(1-Phenylallyloxy)propyl)benzeneC18H20O[α]D20=+1.6 (c 1.11, CHCl3)Source of chirality:Enantioselective allylic substitution reactionAbsolute configuration: (R)

The kinetic resolution of a carbon nucleophile is realized for the first time via Pd-catalyzed asymmetric allylic alkylation with “unstabilized” ketone enolates as the nucleophile, providing both allylated 2,3-disubstituted 2,3-dihydro-4-quinolones and recovered substrates in high yields and high ee (S-factor is 40−145). The application of the methodology in organic synthesis is demonstrated by the ready transformation of an allylated adduct into pyrrolo[3,2-c]quinoline, which features a core structure of biologically active Martinella alkaloids.

A highly diastereo- and enantioselective cyclopropanation reaction was realized in the reaction of acyclic amides with monosubstituted allyl carbonates via Pd-catalysis using a ferrocene ligand with H as a substituent on an oxazoline ring, providing cyclopropane products having three chiral centers in yields of 67−83%, the dr ratio being 4−23:1, and ee being 83−97%. The presence of LiCl is important for the gain of high diastereo- and enantioselectivities of the reaction.

The kinetic resolution of indolines was realized via a Pd-catalyzed allylic substitution reaction by using Trost’s chiral ligand L10, affording optically active indolines and N-allylated indolines in high yields and high enantioselectivities with an S factor up to 59, which provided the first example for the kinetic resolution of nucleophiles via a transition-metal-catalyzed allylic substitution reaction.

The reaction of a glycinate Schiff base with the activated alkyl- and aryl-substituted allylic acetates afforded 4-alkylidenylglutamic acid derivatives in high yields and high enantioselectivities by using Cu/P,N-FcPhox as the catalyst.

Enamines served as carbon-nucleophiles for the first time in the Cu-catalyzed asymmetric propargylic substitution reaction of propargylic acetates, providing corresponding chiral β-ethynyl-substituted ketones in high yields and in good to high enantioselectivity.

The oxidative ring-opening reaction of a variety of activated aziridines by pyridine N-oxide provided α-amino ketones or α-amino aldehydes in good yields.

A new type of biferrocene diphosphine ligand bearing only planar chirality was developed and used in Rh(I)-catalyzed asymmetric hydrogenation of β-keto sulfones, giving the corresponding optically active β-hydroxy sulfones in excellent yields and in 72.4–97.9% ee.(S)-p-TolylsulfinylferroceneC17H16FeOS[α]D20=+314(c0.525,CHCl3)Source of chirality: (−)-menthol(SFc,SS)-1-p-Tolylsulfinyl-2-(diphenylphosphino)ferrocene borane complexC29H28BFeOPS[α]D20=-533(c0.545,CHCl3)Source of chirality: (−)-menthol(R)-2-Diphenylphosphino-ferrocenecarboxaldehyde borane complexC23H22BFeOPS[α]D20=-556(c0.2,CHCl3)Source of chirality: (−)-menthol(R,R)-Bis[2-(diphenylphosphino)ferrocenyl]methanolC45H38Fe2OP2[α]D20=+400(c0.215,CHCl3)Source of chirality: (−)-menthol

Planar chiral [2,2]cyclophane monophosphines are efficient catalyst in the reaction of Morita–Baylis–Hillman adducts with phthalimide. The corresponding allylic substituted products were afforded in high yields and in good to moderate ee.

Desymmetrization of meso-N-sulfonylaziridines with thiols was realized using cinchonine-derived chiral quaternary ammonium salts as the catalyst. The corresponding chiral thio amines were provided in high yields (80–99%) and in good enantioselectivities (40–73% ee).

A series of planar chiral ligands derived from [2.2]paracyclophane were synthesized and applied as catalysts in enantioselective additions of diethylzinc to aldehydes and α,β-unsaturated ketones. When ligand 10 with a dimethyl hydroxymethyl as the substituent was used, the enantioselectivity of the reaction of diethylzinc with aldehydes was much higher than when using ligand 3c with diphenyl hydroxymethyl as the substituent. The situation was the same with the 1,4-addition of diethylzinc to α,β-unsaturated ketones with 63–83% ee being obtained when the hydroxymethyl substituted ligand 7b was used, while almost no enantioselectivity was afforded if ligand 3c was used. The role of planar chirality is also studied.(S,4Rp,13Sp)-4-Formyl-13-(4-iso-propyl-oxazolin-2-yl)[2.2]paracyclophaneC23H25NO2[α]D20=−62.3 (c 0.45, CHCl3)Source of chirality: (S)-valinol(S,4Sp,13Rp)-4-Formyl-13-(4-iso-propyl-oxazolin-2-yl)[2.2]paracyclophaneC23H25NO2[α]D20=+59.6 (c 0.545, CHCl3)Source of chirality: (S)-valinol(S,4Rp,13Sp)-4-Formyl-13-(4-tert-butyl-oxazolin-2-yl)[2.2]paracyclophaneC24H27NO2[α]D20=−34.6 (c 0.36, CHCl3)Source of chirality: (S)-tert-leucinol(S,4Sp,13Rp)-4-Formyl-13-(4-tert-butyl-oxazolin-2-yl)[2.2]paracyclophaneC24H27NO2[α]D20=+186 (c 0.33, CHCl3)Source of chirality: (S)-tert-leucinol(S,4Rp,13Sp)-4-Formyl-13-(4-benzyl-oxazolin-2-yl)[2.2]paracyclophaneC27H25NO2[α]D20=−19.0 (c 0.30, CHCl3)Source of chirality: (S)-phenylaniol(S,4Sp,13Rp)-4-Formyl-13-(4-benzyl-oxazolin-2-yl)[2.2]paracyclophaneC27H25NO2[α]D20=+41.7 (c 0.36, CHCl3)Source of chirality: (S)-phenylaniol(S,4Sp,13Rp)-4-(4-iso-Propyl-oxazoline-2-yl)-13-hydroxylmethyl[2.2]paracyclophaneC23H27NO2[α]D20=−32.5 (c 0.325, CHCl3)Source of chirality: (S)-valinol(S,4Rp,13Sp)-4-(4-iso-Propyl-oxazoline-2-yl)-13-hydroxylmethyl[2.2]paracyclophaneC23H27NO2[α]D20=−123.9 (c 0.355, CHCl3)Source of chirality: (S)-valinol(S,4Rp,13Sp)-4-(4-tert-Butyl-oxazoline-2-yl)-13-hydroxylmethyl[2.2]paracyclophaneC24H29NO2[α]D20=+99.2 (c 0.370, CHCl3)Source of chirality: (S)-tert-leucinol(S,4Sp,13Rp)-4-(4-tert-Butyl-oxazoline-2-yl)-13-hydroxylmethyl[2.2]paracyclophaneC24H29NO2[α]D20=−103.9 (c 0.425, CHCl3)Source of chirality: (S)-tert-leucinol(S,4Sp,13Rp)-4-(4-Benzyl-oxazolin-2-yl)-13-hydroxylmethyl[2.2]paracyclophaneC27H27NO2[α]D20=+116.9 (c 0.395, CHCl3)Source of chirality: (S)-phenylaniol(S,4Rp,13Sp)-4-(4-Benzyl-oxazolin-2-yl)-13-hydroxylmethyl[2.2]paracyclophaneC27H27NO2[α]D20=−79.2 (c 0.365, CHCl3)Source of chirality: (S)-phenylaniol(S,4Sp,13Rp)-4-(4-tert-Butyl-oxazoline-2-yl)-13-(α,α-dimethylhydroxymethyl)[2.2]paracyclophaneC26H33NO2[α]D20=+75.5 (c 0.435, CHCl3)Source of chirality: (S)-tert-leucinol(S,4Sp,13Rp)-4-(4-Benzyl-oxazoIin-2-yl)-13-(α,α-dimethylhydroxymethyl)[2.2]paracyclophaneC29H31NO2[α]D20=+52.5 (c 0.36, CHCl3)Source of chirality: (S)-phenylaniol(S,4Rp,13Sp)-4-(4-Benzyl-oxazolin-2-yl)-13-(α,α-dimethylhydroxymethyl)[2.2]paracyclophaneC29H31NO2[α]D20=+16.2 (c 0.31, CHCl3)Source of chirality: (S)-phenylaniol(4Sp,13Rp)-4-Bromo-13-carboxy[2.2]paracyclophaneC17H15BrO2[α]D20=+46 (c 0.105, CHCl3)Source of chirality: (S)-valinol(4Sp,13Rp)-4-Bromo-N-(1-hydroxy-2-ethyl)[2.2]paracyclophane-13-carboxamideC19H20BrO2[α]D20=−22.7 (c 0.5, CHCl3)Source of chirality: (S)-valinol(4Sp,13Rp)-4-Bromo-N-(1-hydroxy-2-methyl-2-propyl)[2.2]paracyclophane13-carboxamideC21H24BrNO2[α]D20=+32.4 (c 0.51, CHCl3)Source of chirality: (S)-valinol(4Sp,13Rp)-4-Bromo-13-(oxazolin-2-yl)[2.2]paracyclophaneC19H18BrNO[α]D20=+31.3 (c 0.49, CHCl3)Source of chirality: (S)-valinol(4Sp,13Rp)-4-Bromo-13-(4,4-dimethyl-oxazolin-2-yl)[2.2]paracyclophaneC21H22BrNO2[α]D20=+41.1 (c 0.55, CHCl3)Source of chirality: (S)-valinol(4Rp,13Sp)-4-(Oxazolin-2-yl)-13-(α,α-dimethylhydroxymethyl)[2.2]paracyclophaneC22H25NO2[α]D20=−59.0 (c 0.395, CHCl3)Source of chirality: (S)-valinol(4Rp,13Sp)-4-(4,4-Dimethyl-oxazolin-2-yl)-13-(α,α-dimethylhydroxymethyl)[2.2]paracyclophaneC24H29NO2[α]D20=−41.4 (c 0.39, CHCl3)Source of chirality: (S)-valinol

A series of new chiral P,N-ligands with substituents at the benzylic position has been prepared. Their high catalytic activity is shown in the Pd-catalyzed asymmetric Heck reaction and allylic substitution reaction.Graphic2-(2′-Diphenylphosphanyl-benzyl)-(S)-4-isopropyl-4,5-dihydro-oxazoleC25H26NOP[α]D20=−39.7 (c 1.06, CHCl3)Source of chirality: (S)-valineAbsolute configuration: (S)(S)-4-tert-Butyl-2-(2′-diphenylphosphanyl-benzyl)-4,5-dihydro-oxazoleC26H28NOP[α]D20=−32.7 (c 0.504, CHCl3)Source of chirality: (S)-tert-leucineAbsolute configuration: (S)2-(2′-Diphenylphosphanyl-benzyl)-(S)-4-phenyl-4,5-dihydro-oxazoleC28H24NOP[α]D20=−37.9 (c 0.415, CHCl3)Source of chirality: (S)-phenylglycineAbsolute configuration: (S)

The oxidative ring-opening reaction of a variety of activated aziridines by pyridine N-oxide provided α-amino ketones or α-amino aldehydes in good yields.