Efficient Synthesis of (−)‐Corynoline by Enantioselective Palladium‐Catalyzed α‐Arylation with Sterically Hindered Substrates

Rao, Xiaofeng; Li, Nai‐Kai; Bai, Heng; Dai, Chaodi; Wang, Zheng; Tang, Wenjun

doi:10.1002/ange.201807302

Cited by 15 publications

(7 citation statements)

References 77 publications

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“…It should be noted that chiral ligands such as BINAP, DuPhos, and MonoPhos did not provide any desired product. Asymmetric α-arylation 36 to build chiral all-carbon quaternary centers received much attention, and its sterically hindered version compatible with ortho substitution remained a significant challenge. The catalyst Pd−BI-DIME (Pd−L9) allowed facile coupling between aryl ketone 53 and bromoarene 54 to form α-arylation product 55 bearing an all-carbon quaternary center in excellent yield and ee.…”

Section: F Miscellaneous Asymmetric Transformationsmentioning

confidence: 99%

P-Chiral Phosphorus Ligands Based on a 2,3-Dihydrobenzo[d][1,3]oxaphosphole Motif for Asymmetric Catalysis

Senanayake²,

2019

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Conspectus Despite the rapid progress in the field of asymmetric catalysis, the search for new, efficient, and practical asymmetric catalytic transformations to facilitate the green synthesis of chiral natural products and drugs will continue to be a major ongoing effort in organic chemistry. Chiral phosphorus ligands have played a significant role in recent advances in transition-metal-catalyzed asymmetric transformations. However, there remain numerous challenging issues of reactivity and selectivity in catalysis. The development of new and efficient chiral phosphorus ligands with new structural motifs remains highly desirable. P-Chiral phosphorus ligands have been overlooked and are underdeveloped, except for the early success of DIPAMP, introduced first by Knowles in the early 1970s. It was not until the late 1990s that the development of P-chiral phosphorus ligands regained attention with the advent of bisP*, TangPhos, etc. Nonetheless, most P-chiral phosphorus ligands were either difficult to prepare or operationally inconvenient. The development of efficient, practical, and operationally convenient P-chiral phosphorus ligands with new structural motifs remains an important subject of research. This Account introduces the design and development of a series of practical and efficient P-chiral bis- and monophosphorus ligands based on a 2,3-dihydrobenzo[d][1,3]oxaphosphole motif. Their unique structural and physical properties include conformational unambiguousness, high tunability of electronic and steric properties, and operational simplicity as air-stable solids, which make them practical and exceptional ligands for asymmetric catalysis. Chiral bisphosphorus ligands such as MeO-BIBOP (L3), WingPhos (L4), and iPr-BABIBOP (L7) have demonstrated excellent enantioselectivities and unprecedented turnover numbers (TONs) in various asymmetric hydrogenations and other transformations, providing practical and efficient solutions leading to chiral amines, alcohols, carboxylic acids, and α- and β-amino acids. Chiral biaryl monophosphorus ligands, including BI-DIME (L9), AntPhos (L15), iPr–BI-DIME (L11), etc., have proven to be a class of versatile and powerful ligands for a number of catalytic asymmetric transformations, including asymmetric Suzuki–Miyaura coupling, asymmetric palladium-catalyzed dearomative cyclization, asymmetric hydroboration/diboration, asymmetric nickel-catalyzed reductive coupling, asymmetric palladium-catalyzed intramolecular arylation, asymmetric alkene aryloxyarylation, asymmetric α-arylation, asymmetric Heck reaction, and asymmetric nucleophilic addition, providing efficient solutions leading to various synthetically challenging chiral structures such as chiral biaryls, chiral tertiary alcohols, chiral α-amino tertiary boronic esters, and chiral all-carbon quaternary stereocenters. The high enantioselectivities and TONs obtained with these ligands have resulted in the syntheses of several chiral natural products and therapeutic agents in concise and highly efficient manners. While our eff...

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Section: F Miscellaneous Asymmetric Transformationsmentioning

confidence: 99%

P-Chiral Phosphorus Ligands Based on a 2,3-Dihydrobenzo[d][1,3]oxaphosphole Motif for Asymmetric Catalysis

Senanayake²,

2019

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“…The Tang group developed α-arylation of sterically hindered substrates, which is still a challenging task to tackle. 168 Bulky and ortho-substituted aryl halides tend to give products in low yields and ee values. A sterically hindered BI-DIME type ligand performed well in this reaction and gave products in 73−93% yields and ee values in the range of 53−95% (Scheme 54c).…”

Section: ■ Introductionmentioning

confidence: 99%

Asymmetric Transition-Metal Catalysis in the Formation and Functionalization of Metal Enolates

et al. 2019

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This review comprises two major parts, which have chiral metal enolates as their focus. In the first part, we discuss transition-metal-catalyzed conjugate additions leading to chiral enolates, which are then subsequently functionalized by reactions with electrophiles, both further catalyzed or uncatalyzed. The second part deals with base-generated enolates and their use in asymmetric transition-metal-catalyzed processes.

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“…Inspired by this mode of reactivity, and deducing that pyridinylmethanamine can be viewed simply as the core unit of a pyridoxamine, we surmised that chiral aldehyde catalysis might be effective for the asymmetric α-functionalization of pyridinylmethanamines. The chiral pyridinylmethanamine unit is found frequently in biologically active compounds 47 – 49 , chiral ligands 50 – 53 and natural products 54 – 58 , so the preparation of optically active pyridinylmethanamine derivatives is highly valuable work.…”

Section: Resultsmentioning

confidence: 99%

Diastereodivergent chiral aldehyde catalysis for asymmetric 1,6-conjugated addition and Mannich reactions

Wen

Luo

et al. 2020

Nat Commun

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Chiral aldehyde catalysis is a burgeoning strategy for the catalytic asymmetric α-functionalization of aminomethyl compounds. However, the reaction types are limited and to date include no examples of stereodivergent catalysis. In this work, we disclose two chiral aldehyde-catalysed diastereodivergent reactions: a 1,6-conjugate addition of amino acids to para-quinone methides and a bio-inspired Mannich reaction of pyridinylmethanamines and imines. Both the syn- and anti-products of these two reactions can be obtained in moderate to high yields, diastereo- and enantioselectivities. Four potential reaction models produced by DFT calculations are proposed to explain the observed stereoselective control. Our work shows that chiral aldehyde catalysis based on a reversible imine formation principle is applicable for the α-functionalization of both amino acids and aryl methylamines, and holds potential to promote a range of asymmetric transformations diastereoselectively.

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Efficient Synthesis of (−)‐Corynoline by Enantioselective Palladium‐Catalyzed α‐Arylation with Sterically Hindered Substrates

Cited by 15 publications

References 77 publications

P-Chiral Phosphorus Ligands Based on a 2,3-Dihydrobenzo[d][1,3]oxaphosphole Motif for Asymmetric Catalysis

P-Chiral Phosphorus Ligands Based on a 2,3-Dihydrobenzo[d][1,3]oxaphosphole Motif for Asymmetric Catalysis

Asymmetric Transition-Metal Catalysis in the Formation and Functionalization of Metal Enolates

Diastereodivergent chiral aldehyde catalysis for asymmetric 1,6-conjugated addition and Mannich reactions

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