TY - JOUR

T1 - Assembly of (2×C2+C`2)×n Molecular Complexity Using a Sequence of Pt- and Pd-Catalyzed Transformations with Calcium Carbide

AU - Потороченко, Антон Николаевич

AU - Родыгин, Константин Сергеевич

AU - Анаников, Валентин Павлович

PY - 2024/1/22

Y1 - 2024/1/22

N2 - Constructing molecular complexity from simple precursors stands as a cornerstone in contemporary organic synthesis. Systems harnessing easily accessible starting materials, which offer control over stereochemistry and support a modular assembly approach, are particularly in demand. In this research, we utilized calcium carbide, presenting a sustainable pathway to generate acetylene gas – a fundamental C2 building block. We performed a Pt-facilitated linkage of two C2-units sourced from two calcium carbide molecules to craft a conjugated C4 core with exceptional stereoselectivity. As a benchmark, we selected the synthesis of (E,E)-1,4-diiodobuta-1,3-diene, executing it in a two-chamber reactor. Compartmentalization of the reactions across these chambers resulted in the desired product in 85% yield. Furthermore, high-energy polymeric substances were derived by marrying the molecular intricacy between (E,E)-1,4-diiodobuta-1,3-diene and calcium carbide, underpinning a unique C4+C2 assembly blueprint. The structure and morphology of the polymeric material were characterized by IR and NMR spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy. Overall, two complementary 2×C2-to-C4 and (2×C2+C’2)×n assembly schemes were developed using Pt and Pd catalysis.

AB - Constructing molecular complexity from simple precursors stands as a cornerstone in contemporary organic synthesis. Systems harnessing easily accessible starting materials, which offer control over stereochemistry and support a modular assembly approach, are particularly in demand. In this research, we utilized calcium carbide, presenting a sustainable pathway to generate acetylene gas – a fundamental C2 building block. We performed a Pt-facilitated linkage of two C2-units sourced from two calcium carbide molecules to craft a conjugated C4 core with exceptional stereoselectivity. As a benchmark, we selected the synthesis of (E,E)-1,4-diiodobuta-1,3-diene, executing it in a two-chamber reactor. Compartmentalization of the reactions across these chambers resulted in the desired product in 85% yield. Furthermore, high-energy polymeric substances were derived by marrying the molecular intricacy between (E,E)-1,4-diiodobuta-1,3-diene and calcium carbide, underpinning a unique C4+C2 assembly blueprint. The structure and morphology of the polymeric material were characterized by IR and NMR spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy. Overall, two complementary 2×C2-to-C4 and (2×C2+C’2)×n assembly schemes were developed using Pt and Pd catalysis.

KW - (E,E)-1,4-diiodobuta-1,3-diene

KW - calcium carbide

KW - conjugated polymer

KW - metal catalyst

KW - two-chamber reactor

UR - https://www.mendeley.com/catalogue/abbd8248-f392-3f42-b988-d85fbe489379/

U2 - 10.1002/ejoc.202301012

DO - 10.1002/ejoc.202301012

M3 - Article

VL - 27

JO - Liebigs Annalen der Chemie

JF - Liebigs Annalen der Chemie

SN - 1434-193X

IS - 4

M1 - e202301012

ER -