"Back-to-Front" Indole Synthesis using Silver(I) Catalysis: Unexpected C-3 Pyrrole Activation Mode Supported by DFT

TY - JOUR

T1 - "Back-to-Front" Indole Synthesis using Silver(I) Catalysis

T2 - Unexpected C-3 Pyrrole Activation Mode Supported by DFT

AU - Clarke, Aimee K.

AU - Lynam, Jason M.

AU - Taylor, Richard John Kenneth

AU - Unsworth, William Paul

N1 - © 2018 American Chemical Society.

PY - 2018/8/3

Y1 - 2018/8/3

N2 - An efficient silver(I)-catalyzed method is reported for the synthesis of substituted indoles, most notably 5-hydroxy-derivatives, via π-acidic alkyne activation. Most methods for the preparation of indoles involve annulation of a benzene precursor, but the method reported herein is unusual in that pyrrole precursors are used. Density Functional Theory (DFT) studies suggest that these reactions proceed via initial activation of the pyrrole C-3 position before undergoing subsequent rearrangement, contradicting the conventional wisdom that pyrroles are more nucleophilic through C-2.

AB - An efficient silver(I)-catalyzed method is reported for the synthesis of substituted indoles, most notably 5-hydroxy-derivatives, via π-acidic alkyne activation. Most methods for the preparation of indoles involve annulation of a benzene precursor, but the method reported herein is unusual in that pyrrole precursors are used. Density Functional Theory (DFT) studies suggest that these reactions proceed via initial activation of the pyrrole C-3 position before undergoing subsequent rearrangement, contradicting the conventional wisdom that pyrroles are more nucleophilic through C-2.

KW - alkynes

KW - cyclization

KW - indoles

KW - silver(I)

KW - spirocycles

UR - http://www.scopus.com/inward/record.url?scp=85048690716&partnerID=8YFLogxK

U2 - 10.1021/acscatal.8b00745

DO - 10.1021/acscatal.8b00745

M3 - Article

AN - SCOPUS:85048690716

SN - 2155-5435

VL - 8

SP - 6844

EP - 6850

JO - ACS Catalysis

JF - ACS Catalysis

IS - 8

ER -