Mild procedures for interconverting allylic oxygen functionality. Cyclization-induced [3,3] sigmatropic rearrangement of allylic carbamates

1978 ◽  
Vol 100 (15) ◽  
pp. 4822-4834 ◽  
Author(s):  
Larry E. Overman ◽  
Curtis B. Campbell ◽  
Fredrick M. Knoll
Keyword(s):  
Sigmatropic Rearrangement ◽  
Oxygen Functionality

An approach to the synthesis of bruceantin. The synthesis of a tetracyclic intermediate

1989 ◽  
Vol 67 (12) ◽  
pp. 2237-2240 ◽  
Author(s):  
Sultan Darvesh ◽  
Andrew S. Grant ◽  
David I. Magee ◽  
Zdenek Valenta
Keyword(s):  
Sigmatropic Rearrangement ◽  
Terminal Acetylene ◽  
Chiral Centers ◽  
Oxygen Functionality

An intermediate (20) containing four of the five rings and seven of the ten chiral centers of bruceantin (1) was prepared. In a key reaction, 3-iodo-1-trimethylsilyl-5-hexen-1-yne (9) was found to add chemoselectively and stereoselectively to a dianion. The sequence also includes a selective attack by a sulfinate (17) on the terminal acetylene C-atom of the dianion of a keto acetylene, a concomitant cyclization in which the acetylene acts as an electrophile, and the use of the resulting allyl sulfoxide for the introduction of oxygen functionality by a reductive rearrangement. Keywords: bruceantin, sigmatropic rearrangement, stereoselective alkylation.

scholarly journals Copper-Catalyzed Synthesis of Axially Chiral Biaryls with Diaryliodonium Salts as Arylation Reagents

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3223
Author(s):  
Ji-Wei Zhang ◽  
Shao-Hua Xiang ◽  
Shaoyu Li ◽  
Bin Tan
Keyword(s):  
Amino Alcohols ◽  
Sigmatropic Rearrangement ◽  
Synthetic Route ◽  
Mild Conditions ◽  
Good Substrate ◽  
Diaryliodonium Salts ◽  
Axially Chiral

NOBIN and BINAM derivatives harboring biaryl frameworks are recognized as a class of important atropisomers with versatile applications. Here, we present an efficient synthetic route to access such compounds through copper-catalyzed domino arylation of N-arylhydroxylamines or N-arylhydrazines with diaryliodonium salts and [3,3]-sigmatropic rearrangement. This reaction features mild conditions, good substrate compatibility, and excellent efficiency. The practicality of this protocol was further extended by the synthesis of biaryl amino alcohols.

An Umpolung Oxa-[2,3] Sigmatropic Rearrangement Employing Arynes for the Synthesis of Functionalized Enol Ethers

2021 ◽  
Author(s):  
Rahul N. Gaykar ◽  
Malini George ◽  
Avishek Guin ◽  
Subrata Bhattacharjee ◽  
Akkattu T. Biju
Keyword(s):  
Sigmatropic Rearrangement ◽  
Enol Ethers

scholarly journals Imino‐λ 3 ‐iodane and Catalytic Amount of I 2 ‐Mediated Synthesis of N ‐Allylsulfenamides via [2,3]‐Sigmatropic Rearrangement

2020 ◽  
Vol 2020 (41) ◽  
pp. 6433-6439
Author(s):  
Cody L. Makitalo ◽  
Akira Yoshimura ◽  
Gregory T. Rohde ◽  
Irina A. Mironova ◽  
Rosa Y. Yusubova ◽  
...  
Keyword(s):  
Catalytic Amount ◽  
Sigmatropic Rearrangement

Catalyst-Free [2,3]-Sigmatropic Rearrangement Reactions of Photochemically Generated Ammonium Ylides

Synthesis ◽  
2019 ◽  
Vol 51 (23) ◽  
pp. 4348-4358 ◽  
Author(s):  
Fang Li ◽  
Feifei He ◽  
Rene M. Koenigs
Keyword(s):  
Visible Light ◽  
Sigmatropic Rearrangement ◽  
Tertiary Amines ◽  
Amino Esters ◽  
Catalyst Free ◽  
Rearrangement Reaction ◽  
Rearrangement Reactions ◽  
Free Ammonium

The rearrangement reaction of ammonium ylides furnishes valuable α,α-disubstituted amino esters. In this work, we describe the visible-light photolysis reaction of aryldiazoacetates in the presence of tertiary amines that react via a free ammonium ylide in a sigmatropic rearrangement reaction to provide amino esters in moderate to very good yields (33 examples, up to 97% yield).

ChemInform Abstract: Selenoxide Elimination and [2,3]-Sigmatropic Rearrangement

ChemInform ◽  
2010 ◽  
Vol 31 (29) ◽  
pp. no-no
Author(s):  
Yoshiaki Nishibayashi ◽  
Sakae Uemura
Keyword(s):  
Sigmatropic Rearrangement
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