A formal enone α-arylation is described. This metal-free transformation relies on the I(III)-mediated skeletal reorganization of silyl enol ethers and features mild conditions, good yields, and high stereoselectivities for β-substituted enones.
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http://dx.doi.org/10.1021/acs.orglett.1c00251 | DOI Listing |
Nat Commun
November 2024
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, China.
Electronically mismatched Diels-Alder reaction between two electron-deficient components is synthetically useful and yet underdeveloped under thermal conditions. Herein, a photoinduced formal [4 + 2] cycloaddition of enone with a variety of electron-deficient dienes is described. Key to the success of this stepwise methodology relies on a C - C bond cleavage/rearrangement of the cyclobutane based overbred intermediate via diversified mechanistic pathways.
View Article and Find Full Text PDFTetrahedron Lett
April 2024
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
The norcembranoid and cembranoid diterpenoids represent an intriguing class of natural products isolated from marine sources. Their chemical synthesis has been a challenging and exciting field of research over the past two decades, owing largely to their structural complexity. We recently disclosed a total synthesis of a member of this class, ineleganolide, in a 23 step longest linear sequence.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
May 2024
Key Laboratory of Applied Surface and Colloid Chemistry & School of Chemistry and Chemical Engineering, Shaanxi Normal University, 620 West Chang'an Ave, Xi'an, 710119, China.
Herein, we present a unified chemical synthesis of three subgroups of cephalotaxus diterpenoids. Key to the success lies in adopting a synthetic strategy that is inspired by biosynthesis but is opposite in nature. By employing selective one-carbon introduction and ring expansion operations, we have successfully converted cephalotane-type C dinorditerpenoids (using cephanolide B as a starting material) into troponoid-type C norditerpenoids and intact cephalotane-type C diterpenoids.
View Article and Find Full Text PDFAcc Chem Res
March 2024
Key Laboratory of Applied Chemistry of Chongqing Municipality and Chongqing Key Laboratory of Soft-Matter Material Chemistry and Function Manufacturing, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
ConspectusThe development of catalytic activation modes provides a reliable and effective platform for designing new enantioselective reactions and preparing chiral molecules with diverse structures. Chiral aldehyde catalysis is an attractive concept in asymmetric catalysis, which utilizes a chiral aldehyde catalyst to promote the asymmetric hydroamination of allylic amines, the asymmetric α-functionalization of primary amines, or the asymmetric transamination of α-keto esters. Typically, the chiral aldehyde-catalyzed asymmetric α-functionalization of primary amines provides an efficient and straightforward method for the synthesis of α-functionalized chiral amines, which does not require any additional protection or deprotection manipulations of the amine group.
View Article and Find Full Text PDFChemistry
November 2023
Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.
The stereodivergent asymmetric synthesis of 2,5-trans/cis pyrrolidines by 1,3-dipolar cycloaddition using two different types of activated alkenes is described. When ylidene-isoxazolones were employed as dipolarophiles, the Ag/(S,S )-iPr-FcPHOX-catalyzed asymmetric [3+2] cycloaddition of imino lactones proceeded with 2,5-trans selectivity. Subsequent decarboxylation of the isoxazolone rings produced pyrrolidines with 2,5-trans stereoretention.
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