Using Heteroaryl-lithium Reagents as Hydroxycarbonyl Anion Equivalents in Conjugate Addition Reactions with (S,S)-(+)-Pseudoephedrine as Chiral Auxiliary; Enantioselective Synthesis of 3-Substituted Pyrrolidines

2013 ◽  
Vol 78 (2) ◽  
pp. 614-627 ◽  
Author(s):  
Beatriz Alonso ◽  
Marta Ocejo ◽  
Luisa Carrillo ◽  
Jose L. Vicario ◽  
Efraim Reyes ◽  
...  
Keyword(s):  
Conjugate Addition ◽  
Enantioselective Synthesis ◽  
Chiral Auxiliary ◽  
Addition Reactions

scholarly journals Oxazolidinones as Chiral Auxiliaries in the Asymmetric 1,4-Conjugate Addition Reaction Applied to the Total Synthesis of Natural Products: A Supplemental Mini-Review

2018 ◽  
Vol 15 (1) ◽  
pp. 3-20 ◽  
Author(s):  
Vahideh Zadsirjan ◽  
Majid M. Heravi
Keyword(s):  
Total Synthesis ◽  
Biological Activities ◽  
Conjugate Addition ◽  
Chiral Auxiliary ◽  
Addition Reactions ◽  
Chiral Auxiliaries ◽  
Complex Molecules ◽  
Total Syntheses ◽  
Naturally Occurring ◽  
Wide Range

Background: The most frequently used chiral auxiliaries, oxazolidinones (Evans' oxazolidinones) have been employed in 1,4-congugate addition reactions to α,β-unsaturated carbonyl compounds. Supplementary to our previous reports in this mini-review, we attempted to underscore the applications of this strategy in a step (steps) in the total synthesis of some naturally occurring compounds exhibiting diverse biological activities. Objective: In this mini-review, we try to underscore the applications of oxazolidinones (Evans’ oxazolidinones) in 1,4-congugate addition reactions to α,β-unsaturated carbonyl in the total synthesis of some naturally occurring compounds exhibiting diverse biological activities. Conclusion: In spite of well-known superiority of asymmetric catalyzed reactions, the use of auxiliarycontrolled reactions are still considered as commanding, vital and sometimes as only tools in the generation of stereogenic centers during the construction of complex molecules and total synthesis of naturally occurring compounds. The commercial availability, or readily accessibility of a wide variety of chiral amino alcohols as starting materials to synthesize a wide range of oxazolidinones is the merits of them. In addition, the ease of removal and subjection to various and diverse stereoselective reactions make oxazolidinones as the ideal and superior chiral auxiliaries. In this regard, they were successfully used in asymmetric 1,4-conjugate addition reactions with high stereoselectivities. The high degree of asymmetric induction can be attributed to the rigid chelation of N-acyloxazolidinones with metal ions, as well as the covering of one face of the system by the bulkiness of 4-substituent. In summary, in this report, the importance of the applications of chiral oxazolidinones as suitable chiral auxiliaries in the stereoselective, 1,4-conjugate addition reactions in asymmetric synthesis and in particular, the total synthesis of naturally occurring compounds and some complex molecules were underscored. Noticeably, in these total syntheses, this chiral auxiliary is controlling the stereochemistry of a newly created stereogenic center as well as preserving the configuration of other chiral centers, which already have been presented in the precursor. General methods have been established for the attachment of the chiral auxiliary as a moiety to the substrate molecule in high to excellent yields. At the end of these reactions, this auxiliary can be easily removed leaving various desired reactive motifs for the next step in multi-step synthesis.

scholarly journals Catalytic enantioselective synthesis of tetrasubstituted chromanones via palladium-catalyzed asymmetric conjugate arylation using chiral pyridine-dihydroisoquinoline ligands

2020 ◽  
Vol 11 (18) ◽  
pp. 4602-4607 ◽  
Author(s):  
Doohyun Baek ◽  
Huijeong Ryu ◽  
Ji Yeon Ryu ◽  
Junseong Lee ◽  
Brian M. Stoltz ◽  
...  
Keyword(s):  
Conjugate Addition ◽  
Enantioselective Synthesis ◽  
Addition Reactions ◽  
Arylboronic Acids ◽  
Palladium Catalyzed

The first palladium-catalyzed enantioselective conjugate addition reactions of arylboronic acids to 2-substituted chromones with chiral pyridine-dihydroisoquinoline ligands have been developed.

The Rationale for Stereoinduction in Conjugate Addition to Alkylidenemalonates Bearing a Menthol-derived Chiral Auxiliary

Tetrahedron ◽  
2021 ◽  
pp. 132220
Author(s):  
Ken-ichi Yamada ◽  
Shinichi Fujiwara ◽  
Tsubasa Inokuma ◽  
Masayuki Sugano ◽  
Yousuke Yamaoka ◽  
...  
Keyword(s):  
Conjugate Addition ◽  
Chiral Auxiliary

Asymmetric Synthesis of α-Alkylated γ-Lactam via Nickel/8-Quinim-Catalyzed Reductive Alkyl-Carbamoylation of Unactivated Alkene

Synlett ◽  
2021 ◽  
Author(s):  
Xianqing Wu ◽  
Mohini Shrestha ◽  
Yifeng Chen
Keyword(s):  
Functional Group ◽  
Enantioselective Synthesis ◽  
Chiral Auxiliary ◽  
Alkyl Iodide ◽  
General Strategy ◽  
Chemical Bonds ◽  
Mild Conditions ◽  
Chiral Carbon ◽  
Enantioselective Reaction ◽  
Metal Catalyzed

AbstractChiral-auxiliary-mediated synthesis represents the most frequently used synthetic tool for the induction of chirality on α-position of γ-lactams in organic synthesis. However, the general strategy requires the stoichiometric use of chiral reagents with multiple manipulation steps. Transition-metal-catalyzed asymmetric alkene dicarbofunctionalization using readily available substrates under mild conditions allows the simultaneous construction of two vicinal chemical bonds and a chiral carbon center, hence, gain expedient access to chiral heterocycles. Herein, we disclose a Ni-catalyzed enantioselective reaction of 3-butenyl carbamoyl chloride and primary alkyl iodide enabled by a newly designed chiral 8-quinoline imidazoline ligand (8-Quinim). This protocol features broad functional group tolerance and high enantioselectivities, achieving unprecedented synthesis of chiral nonaromatic heterocycles via catalytic reductive protocol.1 Introduction2 Development of 8-Quinim Ligand3 Nickel/8-Quinim-Catalyzed Enantioselective Synthesis of Chiral α-Alkylated γ-Lactam4 Conclusion and Outlook

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