Simple <i>N</i>-Sulfinyl-Based Chiral Sulfur–Olefin Ligands for Rhodium-Catalyzed Asymmetric 1,4-Additions

Feng, Xiujuan; Wang, Shaobin; Wei, Bowen; Yang, Jing; Du, Haifeng

doi:10.1021/ol2009494

Cited by 103 publications

(32 citation statements)

References 62 publications

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“…Only modest results were obtained with chiral diene ligands (see Supporting Information), while no reaction occurred when chiral bisphosphines were used. However, the reaction of 1 a with 3,5‐dimethylphenylboronic acid (1.3 equiv) in the presence of [{Rh(C 2 H 4 ) 2 Cl} 2 ] (2.5 mol %), the sulfur‐alkene L1 (5.0 mol %), and KF (1.5 equiv) in TBME/ t BuCN/MeOH (40:5:1) gave (+)‐ 2 aa in 61 % yield and 91 % ee (entry 1). The diastereomeric product (+)‐ 2 ab was obtained in 11 % yield and 88 % ee .…”

Section: Methodsmentioning

confidence: 99%

Arylative Intramolecular Allylation of Ketones with 1,3‐Enynes Enabled by Catalytic Alkenyl‐to‐Allyl 1,4‐Rhodium(I) Migration

et al. 2017

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Alkenyl‐to‐allyl 1,4‐rhodium(I) migration enables the generation of nucleophilic allylrhodium(I) species by remote C−H activation. This new mode of reactivity was employed in the diastereoselective reaction of arylboron reagents with substrates containing a 1,3‐enyne tethered to a ketone, to give products containing three contiguous stereocenters. The products can be obtained in high enantioselectivities using a chiral sulfur‐alkene ligand.

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Section: Methodsmentioning

confidence: 99%

Arylative Intramolecular Allylation of Ketones with 1,3‐Enynes Enabled by Catalytic Alkenyl‐to‐Allyl 1,4‐Rhodium(I) Migration

et al. 2017

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“…Clearly, the presence of the “flag methyl” group in the olefinic position of ligand 3 has improved significantly the enantioselectivity in the rhodium‐catalysed additions of arylboronic acids to trifluoromethyl ketones, highlighting subtle effects in the steric and electronic reorganizations of the coordinated transition states, Figure . In this sense, although the sulfolefin‐type ligands can coordinate the rhodium in different ways, NMR and RX studies have shown that they generally act as bidentate ligands capable of coordinating the metal through the sulfur and the double bond ,…”

Section: Figurementioning

confidence: 99%

An Efficient and Practical Method for the Enantioselective Synthesis of Tertiary Trifluoromethyl Carbinols

et al. 2018

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An efficient sulfinamide/olefin based chiral ligand, MetSulfolefin, has been developed for the enantioselective rhodium-catalysed addition of aryl-boronic acids to trifluoromethyl ketones. This shelf-stable ligand is insensitive to air, oxygen and moisture, and it is obtained in only two high yielding steps from cheap commercially available (R)-tert-butanesulfinamide. The new ligand tolerates the use of hindered boronic acids and leads to the formation of a series of chiral trifluoromethylsubstituted tertiary carbinols in high yields and excellent enantioselectivities (up to > 99% ee).

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“…[23] Only modest results were obtained with chiral diene ligands [24] (see Supporting Information), while no reaction occurred when chiral bisphosphines were used. However, the reaction of 1a with 3,5dimethylphenylboronic acid (1.3 equiv) in the presence of [{Rh(C 2 H 4 ) 2 Cl} 2 ]( 2.5 mol %), the sulfur-alkene L1 [25] (5.0 mol %), and KF (1.5 equiv) in TBME/tBuCN/MeOH (40:5:1) gave (+ +)-2aa [17] in 61 %y ield and 91 % ee (entry 1). Thed iastereomeric product (+ +)-2ab was obtained in 11 % yield and 88 % ee.…”

Section: Angewandte Chemiementioning

confidence: 99%

Arylative Intramolecular Allylation of Ketones with 1,3‐Enynes Enabled by Catalytic Alkenyl‐to‐Allyl 1,4‐Rhodium(I) Migration

et al. 2017

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Alkenyl-to-allyl 1,4-rhodium(I) migration enables the generation of nucleophilic allylrhodium(I) species by remote CÀHa ctivation. This new mode of reactivity was employed in the diastereoselective reaction of arylboron reagents with substrates containing a1 ,3-enyne tethered to ak etone,t og ive products containing three contiguous stereocenters.T he products can be obtained in high enantioselectivities using ac hiral sulfur-alkene ligand.CatalyticCÀHfunctionalizationshave revolutionized chemical synthesis by providing powerful new tools for bond construction.[1] However,acritical objective for the advancement of this field is its application to amore diverse range of transformations.N ucleophilic allylations [2] are important reactions that could benefit from C À Hf unctionalization principles.M ost typically,t hese processes have employed allylmetal(loid) reagents such as allyltin, allylboron, or allylsilicon compounds.[2] Theg eneration of nucleophilic allylmetal species by the activation of allylic C À Hb onds would bypass the need to prepare such reagents and potentially increase efficiencyb ys treamlining synthetic sequences.This strategy would also be avaluable complement to nucleophilic allylations involving migratory insertions of allenes, [3,4] theu se of simple p-unsaturated compounds in hydrogenative or redox-triggered additions, [5,6] hetero-ene reactions, [7] and Prins reactions.[8]Although generating electrophilic allylmetal species by allylic CÀHa ctivation is well-known, [9,10] there is,t oo ur knowledge,l imited precedent for corresponding processes that provide nucleophilic allylmetals.[11] Very recently,t he groups of Schneider, [11a] Kanai, [11b] and Mita and Sato [11c] described the formation and trapping of nucleophilic allylmetal species from simple hydrocarbons.I nv iew of the nucleophilic character of allylrhodium(I) species, [4a, 12] we envisaged that activation of ar emote CÀHb ond by 1,4-rhodium(I) migration [12d, 13, 14] could also achieve this goal. Specifically,r hodium(I)-catalyzed reaction of an arylboron reagent with the alkyne of a1 ,3-enyne would provide the alkenylrhodium species A (Scheme 1). This intermediate could then undergo a1 ,4-rhodium(I) shift to the cis-allylic substituent to give the allylrhodium(I) species B,which could be trapped by an electrophile.This approach was expected to be challenging,given that there is only very limited precedent for rhodium(I) to migrate to C(sp 3 )c enters.[12d,14k,m] Nevertheless,t he generation of electrophilic allylrhodium(III) species by as imilar strategy in our rhodium(III)-catalyzed oxidative annulations of 1,3-enynes provided some encouragement.[10] Herein, we describe the implementation of this strategy in arylative intramolecular allylations of ketones to give stereochemically complex fused bicycles with high diastereoselectivities.P reliminary results of enantioselective reactions are also provided.This study began with the reaction of the enynone 1a with 3,5-dimethylphenyl pinacol boronate (1.3 equiv), [...

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Simple N-Sulfinyl-Based Chiral Sulfur–Olefin Ligands for Rhodium-Catalyzed Asymmetric 1,4-Additions

Cited by 103 publications

References 62 publications

Arylative Intramolecular Allylation of Ketones with 1,3‐Enynes Enabled by Catalytic Alkenyl‐to‐Allyl 1,4‐Rhodium(I) Migration

Arylative Intramolecular Allylation of Ketones with 1,3‐Enynes Enabled by Catalytic Alkenyl‐to‐Allyl 1,4‐Rhodium(I) Migration

An Efficient and Practical Method for the Enantioselective Synthesis of Tertiary Trifluoromethyl Carbinols

Arylative Intramolecular Allylation of Ketones with 1,3‐Enynes Enabled by Catalytic Alkenyl‐to‐Allyl 1,4‐Rhodium(I) Migration

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