Organocatalytic Enantioselective 1,8-Addition for the Synthesis of Chiral Tetraarylmethanes from 2-Naphthol/Naphthalen-2-amine-Based Tertiary Alcohols

Liu, Meiwen1,2; Shen, Boming1,2; Liu, Chang1,2; Yu, Peiyuan1,2; Li, Pengfei1,2

2023-06-01

10.1021/jacs.3c05107

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Catalyticenantioselective construction of optically active tetraarylmethanesremains a challenging issue in the field of asymmetric synthesis becauseof the overwhelming steric hindrance and formidable stereocontrolthat existed in construction of the all-aryl-substituted quaternarycarbon stereocenter. Here, we reported an organocatalytic asymmetricsynthesis of chiral tetraarylmethanes from racemic tertiary alcohols.With the aid of a chiral phosphoric acid catalyst, 6-methylenenaphthalen-2(6H)-ones were generated in situ from 6-(hydroxydiarylmethyl)naphthalen-2-ols,followed by stereoselective 1,8-conjugate addition to afford the correspondingtetraarylmethanes in high to excellent yields with high enantioselectivities.Furthermore, the scope of tertiary alcohols has been successfullyenlarged to 6-(hydroxydiphenylmethyl)naphthalen-2-amines. Notably,it is the first time to use 2-naphthol/naphthalen-2-amine unit asthe auxiliary group to in situ generate & alpha;,& beta;,& gamma;,& delta;,& epsilon;,& zeta;-conjugatesystems, which have been successfully involved in organocatalyticremote stereocontrolled 1,8-conjugate addition reactions. Particularly,organocatalytic stereoconvergent formal nucleophilic substitutionreaction of triarylmethanols has been achieved for the asymmetricconstruction of chiral tetraarylmethanes. In addition, DFT calculationshave been applied to provide guidance for the design of additionaltertiary alcohols and understand the origin of stereoselectivity.

SCI ; EI ; IC ; CCR

英语

NI论文

第一 ; 通讯

Shenzhen Innovation of Science and Technology Commission[20200925151614002] ; Guangdong Innovative Program[2019BT02Y335] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Shenzhen Higher Education Institution Stable Support Plan[20200925152921001] ; National Natural Science Foundation of China[22171130]

Chemistry

Chemistry, Multidisciplinary

WOS:001016719700001

AMER CHEMICAL SOC

20232814384429

Addition reactions ; Amines ; Design for testability ; Enantioselectivity ; Substitution reactions

Chemistry:801 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Coll Sci, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China

Liu, Meiwen,Shen, Boming,Liu, Chang,et al. Organocatalytic Enantioselective 1,8-Addition for the Synthesis of Chiral Tetraarylmethanes from 2-Naphthol/Naphthalen-2-amine-Based Tertiary Alcohols[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2023,145(26):14562-14569.

Liu, Meiwen,Shen, Boming,Liu, Chang,Yu, Peiyuan,&Li, Pengfei.(2023).Organocatalytic Enantioselective 1,8-Addition for the Synthesis of Chiral Tetraarylmethanes from 2-Naphthol/Naphthalen-2-amine-Based Tertiary Alcohols.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,145(26),14562-14569.

Liu, Meiwen,et al."Organocatalytic Enantioselective 1,8-Addition for the Synthesis of Chiral Tetraarylmethanes from 2-Naphthol/Naphthalen-2-amine-Based Tertiary Alcohols".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145.26(2023):14562-14569.