Chiral phosphoric acid-catalyzed regio- and enantioselective reactions of functionalized propargylic alcohols

Qian, Chenxiao1,2; Liu, Meiwen1; Sun, Jianwei2; Li, Pengfei1

2022

10.1039/d1qo01864g

Organic Chemistry Frontiers   影响因子和分区

2052-4129

Propargylic alcohols have been known as useful substrates in a wide range of asymmetric reactions. In particular, chiral phosphoric acid (CPA) catalyzed reactions of functionalized propargylic alcohols have opened robust access to axially chiral tetrasubstituted allenes and their related derivatives. However, these types of propargylic alcohols have been essentially limited to the structures that could form quinone methides or methide indoles. Here, we expand the scope of propargylic alcohols and the power of CPA catalysis. With the established system, racemic 3-alkynyl-3-hydroxyisoindolinones reacted efficiently to form diverse spirocyclic heterocycles with high enantioselectivity. Regiodivergence was also observed with different indole nucleophiles. Importantly, the key covalently bonded CPA adduct was isolated, characterized, and further confirmed to be chemically competent, and a possible covalent activation mode was proposed accordingly.

SCI ; EI

英语

第一 ; 通讯

Shenzhen Innovation of Science and Technology Commission[20200925151614002] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Organic

WOS:000745099800001

ROYAL SOC CHEMISTRY

20221011770290

Catalysis ; Enantioselectivity ; Hydrocarbons ; Phosphoric acid ; Quinone

Energy Storage:525.7 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2

Web of Science

1.Southern Univ Sci & Technol, Coll Sci, Shenzhen Grubbs Inst, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Coll Sci, Guangdong Prov Key Lab Catalysis, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
3.Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Clear Water Bay, Hong Kong, Peoples R China

Qian, Chenxiao,Liu, Meiwen,Sun, Jianwei,et al. Chiral phosphoric acid-catalyzed regio- and enantioselective reactions of functionalized propargylic alcohols[J]. Organic Chemistry Frontiers,2022,9:1234-1240.

Qian, Chenxiao,Liu, Meiwen,Sun, Jianwei,&Li, Pengfei.(2022).Chiral phosphoric acid-catalyzed regio- and enantioselective reactions of functionalized propargylic alcohols.Organic Chemistry Frontiers,9,1234-1240.

Qian, Chenxiao,et al."Chiral phosphoric acid-catalyzed regio- and enantioselective reactions of functionalized propargylic alcohols".Organic Chemistry Frontiers 9(2022):1234-1240.