TY - JOUR

T1 - Adamantylfuroylphosphonates: Synthesis and Further Transformations

AU - Певзнер, Леонид

AU - Петров, Михаил Львович

AU - Степаков, Александр Владимирович

PY - 2025/5/1

Y1 - 2025/5/1

N2 - Methods for the synthesis of 5-(adamantan-1-yl)furan-2- and -3-carboxylic acids were developed. Phosphorylation of the acid chlorides of these acids with triethyl phosphite yielded stable furoylphosphonates, which then reacted with ethoxycarbonylmethylenetriphenylphosphorane to form 3-[(5-adamantan-1-yl)furanyl]-3-(diethoxyphosphoryl)acrylates. Bromination of the methyl group of these compounds with N-bromosuccinimide provided bromomethyl and dibromomethyl derivatives. The latter were converted under mild conditions to the corresponding aldehydes, which in turn reacted with hydrazine to give adamantylated derivatives of dihydrofuro[2,3-d][1,2]diazepine. Further treatment of bromomethyl derivative with thiourea and subsequent hydrolysis of the resulting thiouronium salt led to the formation of 4,7-dihydro-5H-thiopyrano[3,4-b]furan containing an adamantyl moiety.

AB - Methods for the synthesis of 5-(adamantan-1-yl)furan-2- and -3-carboxylic acids were developed. Phosphorylation of the acid chlorides of these acids with triethyl phosphite yielded stable furoylphosphonates, which then reacted with ethoxycarbonylmethylenetriphenylphosphorane to form 3-[(5-adamantan-1-yl)furanyl]-3-(diethoxyphosphoryl)acrylates. Bromination of the methyl group of these compounds with N-bromosuccinimide provided bromomethyl and dibromomethyl derivatives. The latter were converted under mild conditions to the corresponding aldehydes, which in turn reacted with hydrazine to give adamantylated derivatives of dihydrofuro[2,3-d][1,2]diazepine. Further treatment of bromomethyl derivative with thiourea and subsequent hydrolysis of the resulting thiouronium salt led to the formation of 4,7-dihydro-5H-thiopyrano[3,4-b]furan containing an adamantyl moiety.

KW - 4,7-dihydro-5H-thiopyrano[3,4-b]furans

KW - Wittig reaction

KW - adamantanylfurancarboxylic acids

KW - dihydrofuro[2,3-d][1,2]diazepines

KW - furaldehyde acetates

KW - furoylphosphonates

KW - hydrolysis

KW - radical bromination

UR - https://www.mendeley.com/catalogue/034509b5-ea0e-3542-94a7-a30526101215/

U2 - 10.1134/S1070363225600584

DO - 10.1134/S1070363225600584

M3 - Article

VL - 95

SP - 1093

EP - 1103

JO - Russian Journal of General Chemistry

JF - Russian Journal of General Chemistry

SN - 1070-3632

IS - 5

ER -