Copper-Catalyzed Reductive Ireland-Claisen Rearrangements of Propargylic Acrylates and Allylic Allenoates

Guo, Siyuan1,2,3,4; Wong, Kong Ching1,2,3,4; Scheeff, Stephan1,2,3,4; He, Zhuo1,2,3,4; Chan, Wesley Ting Kwok5; Low, Kam-Hung1,2,3,4; Chiu, Pauline1,2,3,4

2021-12-01

10.1021/acs.joc.1c02455

JOURNAL OF ORGANIC CHEMISTRY   影响因子和分区

0022-3263

1520-6904

The copper-catalyzed reductive Ireland-Claisen rearrangement of propargylic acrylates led to 3,4-allenoic acids. The use of silanes or pinacolborane as stoichiometric reducing agents and triethylphosphite as a ligand facilitated the divergent and complementary selectivity for the synthesis of diastereomeric anti- and syn-rearranged products, respectively. Copper-catalyzed reductive Ireland-Claisen rearrangement of allylic 2,3-allenoates proceeded effectively only when pinacolborane was used as a reductant to generate various 1,5-dienes in excellent yields and with good diastereoselectivities in some cases. Mechanistic studies showed that the silyl and boron enolates, rather than the copper enolate, underwent a stereospecific rearrangement via a chairlike transition state to afford the corresponding Claisen rearrangement products.

SCI ; EI

英语

通讯

State Key Laboratory of Synthetic Chemistry, National Natural Science Foundation of China General Fund[21672179]

Chemistry

Chemistry, Organic

WOS:000734297100001

AMER CHEMICAL SOC

CHEMISTRY

Web of Science

1.Univ Hong Kong, Dept Chem, Hong Kong, Peoples R China
2.Univ Hong Kong, State Key Lab Synthet Chem, Hong Kong, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518000, Peoples R China
4.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518000, Peoples R China
5.Hong Kong Polytech Univ, Dept Appl Biol & Chem Technol, Hong Kong, Peoples R China

Guo, Siyuan,Wong, Kong Ching,Scheeff, Stephan,et al. Copper-Catalyzed Reductive Ireland-Claisen Rearrangements of Propargylic Acrylates and Allylic Allenoates[J]. JOURNAL OF ORGANIC CHEMISTRY,2021,87(1).

Guo, Siyuan.,Wong, Kong Ching.,Scheeff, Stephan.,He, Zhuo.,Chan, Wesley Ting Kwok.,...&Chiu, Pauline.(2021).Copper-Catalyzed Reductive Ireland-Claisen Rearrangements of Propargylic Acrylates and Allylic Allenoates.JOURNAL OF ORGANIC CHEMISTRY,87(1).

Guo, Siyuan,et al."Copper-Catalyzed Reductive Ireland-Claisen Rearrangements of Propargylic Acrylates and Allylic Allenoates".JOURNAL OF ORGANIC CHEMISTRY 87.1(2021).