Enantioselective synthesis of peperomins A, C, D, and analogs — Examination of diastereoselective cuprate conjugate additions to N-enoyl-4-diphenylmethyl-2-oxazolidinones

2001 ◽  
Vol 79 (11) ◽  
pp. 1546-1555 ◽  
Author(s):  
Mukund P Sibi ◽  
Michael D Johnson ◽  
T Punniyamurthy
Keyword(s):  
Total Synthesis ◽  
Conjugate Addition ◽  
Enantioselective Synthesis ◽  
Conjugate Additions

A concise and general route to secolignans has been developed. The first total synthesis of secolignans peperomin A (1a), peperomin C (1b), and peperomin D (1c) was accomplished in ~28% overall yield over five synthetic steps. Peperomin analogs (1d) and (1e), possessing two differentially substituted aryl groups, were synthesized by a highly selective conjugate addition. The overall yield for the analogs 1d and 1e were 27 and 26%, respectively.Key words: peperomins, secoliganans, conjugate additions, 4-diphenylmethyl-oxazolidin-2-one.

scholarly journals Asymmetric total synthesis of a putative sex pheromone component from the parasitoid wasp Trichogramma turkestanica

2014 ◽  
Vol 10 ◽  
pp. 761-766 ◽  
Author(s):  
Danny Geerdink ◽  
Jeffrey Buter ◽  
Teris A van Beek ◽  
Adriaan J Minnaard
Keyword(s):  
Sex Pheromone ◽  
Total Synthesis ◽  
Parasitoid Wasp ◽  
Conjugate Addition ◽  
Enantioselective Synthesis ◽  
Pheromone Component ◽  
Asymmetric Total Synthesis ◽  
Catalytic Asymmetric ◽  
Key Steps

Virgin females of the parasitoid wasp Trichogramma turkestanica produce minute amounts of a sex pheromone, the identity of which has not been fully established. The enantioselective synthesis of a putative component of this pheromone, (6S,8S,10S)-4,6,8,10-tetramethyltrideca-2E,4E-dien-1-ol (2), is reported as a contribution to this identification. Catalytic asymmetric conjugate addition of methylmagnesium bromide and stereoselective Horner–Wadsworth–Emmons olefinations are used as the key steps, and 2 was obtained in 16 steps with an overall yield of 4.4%.

Enantioselective palladium catalyzed conjugate additions of ortho-substituted arylboronic acids to β,β-disubstituted cyclic enones: total synthesis of herbertenediol, enokipodin A and enokipodin B

2014 ◽  
Vol 12 (31) ◽  
pp. 5883-5890 ◽  
Author(s):  
Jeffrey Buter ◽  
Renée Moezelaar ◽  
Adriaan J. Minnaard
Keyword(s):  
Total Synthesis ◽  
Natural Product ◽  
Conjugate Addition ◽  
Natural Product Synthesis ◽  
Conjugate Additions ◽  
Arylboronic Acids ◽  
Cyclic Enones ◽  
Palladium Catalyzed

Palladium catalyzed asymmetric conjugate addition of ortho-substituted arylboronic acids to cyclic enones and its application in natural product synthesis.

Pursuit of Enantioselective Synthesis of Heterocycle-Bearing ­Stereocenters: The Development of a Stereocontrolled BINOL-­Catalyzed Conjugate Addition of Organoboron Nucleophiles

Synlett ◽  
2017 ◽  
Vol 28 (16) ◽  
pp. 2093-2109 ◽  
Author(s):  
Jeremy May ◽  
Thien Nguyen ◽  
Truong Nguyen ◽  
Phong Le ◽  
Po-An Chen ◽  
...  
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Functional Groups ◽  
Conjugate Addition ◽  
Enantioselective Synthesis ◽  
Mechanistic Studies ◽  
Synthetic Strategy ◽  
Iterative Development

This account chronicles the iterative development of an enantioselective conjugate addition of organoboron nucleophiles to α,β-unsaturated enones and enals catalyzed by BINOL derivatives. Beginning with a specific application of this transformation to the total synthesis of the flinderole alkaloids, the transformation progressed to encompass a much larger scope of heterocycle-substituted electrophiles. The next phase saw progress toward the use of a broader scope of functional nucleophiles, with application in a strategy to synthesize discoipyrrole D. At each stage of this chronologically organized discussion, key problems, hypotheses, and solutions are presented to show the sources of discovery and solutions to problems as the catalyst and other reaction components were made more reactive. The interplay of target-directed reaction development, efforts to increase the scope of compatible functional groups, mechanistic studies, and empirical exploration is described to illustrate sources of chemical discovery.1 Introduction2 Synthesis of the Flinderole Natural Products3 Indole-Bearing Stereocenters4 Heteroaryl-Bearing Stereocenters5 Bis-Heteroaryl Stereocenters6 Synthetic Strategy for Discoipyrrole D7 Bis-Aryl Stereocenters8 Remaining Challenges9 Conclusion

Asymmetric conjugate additions of 2-substituted benzofuran-3(2H)-ones to α,β-unsaturated ketones catalyzed by chiral copper complexes

2017 ◽  
Vol 15 (19) ◽  
pp. 4191-4198 ◽  
Author(s):  
Haojiang Wang ◽  
Yifeng Wang ◽  
Cheng Zhang ◽  
Yidong Jiang ◽  
Mingming Chu ◽  
...  
Keyword(s):  
Copper Complexes ◽  
Conjugate Addition ◽  
Conjugate Additions ◽  
Unsaturated Ketones

A highly enantioselective conjugate addition of 2-substituted benzofuran-3(2H)-ones to α,β-unsaturated ketones promoted by chiral copper complexes has been developed.

Total Synthesis of (±)-α- and β-Lycoranes by Sequential Chemoselective Conjugate Addition−Stereoselective Nitro-Michael Cyclization of an ω-Nitro-α,β,ψ,ω-unsaturated Ester

2003 ◽  
Vol 5 (7) ◽  
pp. 1123-1126 ◽  
Author(s):  
Tomohisa Yasuhara ◽  
Katsumi Nishimura ◽  
Mitsuaki Yamashita ◽  
Naoshi Fukuyama ◽  
Ken-ichi Yamada ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Conjugate Addition ◽  
Unsaturated Ester

scholarly journals A concise enantioselective synthesis of the guaiane sesquiterpene (−)-oxyphyllol

2013 ◽  
Vol 9 ◽  
pp. 2028-2032 ◽  
Author(s):  
Martin Zahel ◽  
Peter Metz
Keyword(s):  
Total Synthesis ◽  
Enantioselective Synthesis ◽  
Englerin A ◽  
Epoxide Opening

(−)-Oxyphyllol was prepared in only 4 steps from an epoxy enone that already served as an intermediate for the total synthesis of the anticancer guaiane (−)-englerin A. A regio- and diastereoselective Co(II)-catalyzed hydration of the olefin and a transannular epoxide opening were used as the key 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.

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