Stereochemical Control via Chirality Pairing: Stereodivergent Syntheses of Enantioenriched Homoallylic Alcohols

Gao, Shang1; Duan, Meng2,3,4; Liu, Jiaming1; Yu, Peiyuan3,4; Houk, Kendall N.2; Chen, Ming1

2021-10-01

10.1002/anie.202107004

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

We report herein the development of stereodivergent syntheses of enantioenriched homoallylic alcohols using chiral nonracemic alpha-CH(2)Bpin-substituted crotylboronate. Chiral phosphoric acid (S)-A-catalyzed asymmetric allyl addition with the reagent gave Z-anti-homoallylic alcohols with excellent enantioselectivities and Z-selectivities. When the enantiomeric acid catalyst (R)-A was utilized, the stereoselectivity was completely reversed and E-anti-homoallylic alcohols were obtained with high E-selectivities and excellent enantioselectivities. By pairing the chirality of the boron reagent with the catalyst, two complementary stereoisomers of chiral homoallylic alcohols can be obtained selectively from the same boron reagent. DFT computational studies were conducted to probe the origins of the observed stereoselectivity. These reactions generate highly enantioenriched homoallylic alcohol products that are valuable for rapid construction of polyketide structural frameworks.

chiral phosphoric acid chirality pairing homoallylic alcohols stereodivergent synthesis

SCI ; EI

英语

NI论文

其他

National Science Foundation["OCI-1053575","CHE-2042353","CHE-1764328"] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000703320500001

WILEY-V C H VERLAG GMBH

20214010988913

Boron ; Catalysts ; Chirality ; Enantioselectivity ; Ketones ; Stereoselectivity

Nonferrous Metals and Alloys excluding Alkali and Alkaline Earth Metals:549.3 ; Chemistry:801 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Atomic and Molecular Physics:931.3

CHEMISTRY

Web of Science

1.Auburn Univ, Dept Chem & Biochem, Auburn, AL 36849 USA
2.Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
4.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Gao, Shang,Duan, Meng,Liu, Jiaming,et al. Stereochemical Control via Chirality Pairing: Stereodivergent Syntheses of Enantioenriched Homoallylic Alcohols[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2021,60:24096-24106.

Gao, Shang,Duan, Meng,Liu, Jiaming,Yu, Peiyuan,Houk, Kendall N.,&Chen, Ming.(2021).Stereochemical Control via Chirality Pairing: Stereodivergent Syntheses of Enantioenriched Homoallylic Alcohols.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,60,24096-24106.

Gao, Shang,et al."Stereochemical Control via Chirality Pairing: Stereodivergent Syntheses of Enantioenriched Homoallylic Alcohols".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60(2021):24096-24106.