15466-96-3Relevant academic research and scientific papers
Total synthesis of (+)-ar -macrocarpene
Khatua, Arindam,Niyogi, Sovan,Bisai, Vishnumaya
supporting information, p. 7140 - 7143 (2019/08/07)
This report features the first catalytic asymmetric total synthesis of a sesquiterpene, (+)-ar-macrocarpene (1), in 7 steps with 42.1% overall yields from commercially available inexpensive 5,5-dimethylcyclohexane 1,3-dione. This strategy relies on a key [3,3]-sigmatropic rearrangement effecting reductive transposition through allylic diazene rearrangement (ADR) in a single step from intermediate allylic alcohol (+)-12 under the Mitsunobu reaction conditions with o-nitrobenzenesulfonyl hydrazide (o-NBSH). Enantioselective reduction of α-bromo vinylogous ester 16 under the Corey-Bakshi-Shibata reduction conditions forges the required stereocenter in the allylic alcohol (+)-12 in a highly enantioenriched manner (95% ee).
Synthesis of 2-azaspiro[4.6]undec-7-enes from N -tosyl- N -(3-arylpropargyl)-tethered 3-methylcyclohex-2-en-1-ols
Yeh, Ming-Chang P.,Liang, Chia-Jung,Fan, Chern-Wei,Chiu, Wei-Hang,Lo, Jun-Yuan
, p. 9707 - 9717,11 (2012/12/12)
The FeCl3-promoted synthesis of 2-azaspiro[4.6]undec-7-ene rings proceeds via ring expansion/cyclization/chlorination of N-tosyl-N-(3- arylpropargyl)-tethered 6-methylbicyclo[4.1.0]heptan-2-ols. This azaspirocyclic ring skeleton can also be obtained in one pot from the tert-butyldimethylsilyl- protected N-tosyl-N-(3-arylpropargyl)-tethered 3-methylcyclohex-2-en-1-ols and diethylzinc/diiodomethane.
A general enantioselective route to the chamigrene natural product family
White, David E.,Stewart, Ian C.,Seashore-Ludlow, Brinton A.,Grubbs, Robert H.,Stoltz, Brian M.
experimental part, p. 4668 - 4686 (2010/08/13)
Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.
The catalytic asymmetric total synthesis of elatol
White, David E.,Stewart, Ian C.,Grubbs, Robert H.,Stoltz, Brian M.
, p. 810 - 811 (2008/09/20)
Described in this report is the first total synthesis of elatol, a halogenated sesquiterpene in the chamigrene natural product family. The key disconnections in our synthetic approach include an enantioselective decarboxylative allylation to form the all-carbon quaternary stereocenter and a ring-closing olefin metathesis to concomitantly form the spirocyclic core as well as the fully substituted chlorinated olefin. This strategy represents a general platform for accessing the chamigrene natural product family, as demonstrated by the synthesis of (+)-laurencenone B as an intermediate in our route. Copyright
Iron(III) tosylate in the preparation of dimethyl and diethyl acetals from ketones and β-keto enol ethers from cyclic β-diketones
Mansilla, Horacio,Afonso, Maria M.
, p. 2607 - 2618 (2008/12/22)
An efficient method for conversion of ketones to their corresponding dimethyl and diethyl acetals and of cyclic β-diketones into β-keto enol ethers using Fe(OTs)3 as a catalyst is described. Copyright Taylor & Francis Group, LLC.
