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The highly regiospecific synthesis and crystal structure determination of 1,1?-2,5? substituted ring-locked ferrocenes

The highly regiospecific synthesis and crystal structure determination of 1,1?-2,5? substituted ring-locked ferrocenes
The highly regiospecific synthesis and crystal structure determination of 1,1?-2,5? substituted ring-locked ferrocenes
1,1'-Ferrocene biscarboxaldehyde (1) has been prepared and the aldehyde groups were subsequently protected with acetal groups to produce 1,1'-bisacetalferrocene (2). A ring-locked ferrocene was synthesised by further derivatisation of the cyclopentadiene rings at the 2,2' positions with phosphine substituents to produce 2,2'-bis-(acetal)-1,1'-diphenylphosphinoferrocene (3), which was subsequently coordinated to either a nickel chloride (5) or nickel bromide (6) metal centre. The ring-locked ferrocene complexes produced 2,5'-bis-(acetal)-1,1'-diphenylphosphinoferrocene substitution patterns. The acetal protecting groups of 2,2'-bis-(acetal)-1,1'-diphenylphosphinoferrocene were removed to produce 1,1'-bis-carboxaldehyde-2,2'-diphenylphosphinoferrocene (4). The Cp rings of 1,1'-bisacetalferrocene were also further derivatised at the 2,2' positions with a silane to produce the ring-locked 1,1'-siloxane-2,5'-bisacetalferrocenophane (7). The acetal protecting groups were removed from this to produce 1,1'-siloxane-2,5'- ferrocenophanecarboxaldehyde (8). For both the phosphine and siloxane electrophiles, the substitution on the Cp rings gives chiral products (obtained as racemic mixtures). Due to the highly regioselective nature of the reaction and diastereoselectivity in the products only C(2)-symmetric compounds were observed without the presence of meso diastereoisomers. Subsequent ring-locking forced the Cp rings to rotate, leading to 1,1'-ring-locked ferrocenes with 2,5'-arrangement of the acetal groups (i.e. on opposite faces of the ferrocene unit).
1, 1? 2, 5?-ferrocene derivatives, ortholithiation, ferroceneophane, ring-locked, regiospecific, chiral
0022-328X
2020-2028
Connell, Arthur
14db3268-a050-49a5-bb3d-a77103ab596c
Holliman, Peter J.
6a747393-e1fa-485f-aa9e-b71c7cd31e56
Butler, Ian R.
a3e83fb2-442a-47c7-95c8-756a9a5e9f79
Male, Louise
89b88c4f-2308-4b94-8f3a-2dc537a66533
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, Peter N.
48f162d1-d6ce-43c1-aeef-d58b3ec702b8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Clegg, William
5b1994af-8799-4402-9c01-8479959de00b
Russo, Luca
9ba8498e-b3c4-4202-889a-493162e5729b
Connell, Arthur
14db3268-a050-49a5-bb3d-a77103ab596c
Holliman, Peter J.
6a747393-e1fa-485f-aa9e-b71c7cd31e56
Butler, Ian R.
a3e83fb2-442a-47c7-95c8-756a9a5e9f79
Male, Louise
89b88c4f-2308-4b94-8f3a-2dc537a66533
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, Peter N.
48f162d1-d6ce-43c1-aeef-d58b3ec702b8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Clegg, William
5b1994af-8799-4402-9c01-8479959de00b
Russo, Luca
9ba8498e-b3c4-4202-889a-493162e5729b

Connell, Arthur, Holliman, Peter J., Butler, Ian R., Male, Louise, Coles, Simon J., Horton, Peter N., Hursthouse, Michael B., Clegg, William and Russo, Luca (2009) The highly regiospecific synthesis and crystal structure determination of 1,1?-2,5? substituted ring-locked ferrocenes. Journal of Organometallic Chemistry, 694 (13), 2020-2028. (doi:10.1016/j.jorganchem.2009.01.049).

Record type: Article

Abstract

1,1'-Ferrocene biscarboxaldehyde (1) has been prepared and the aldehyde groups were subsequently protected with acetal groups to produce 1,1'-bisacetalferrocene (2). A ring-locked ferrocene was synthesised by further derivatisation of the cyclopentadiene rings at the 2,2' positions with phosphine substituents to produce 2,2'-bis-(acetal)-1,1'-diphenylphosphinoferrocene (3), which was subsequently coordinated to either a nickel chloride (5) or nickel bromide (6) metal centre. The ring-locked ferrocene complexes produced 2,5'-bis-(acetal)-1,1'-diphenylphosphinoferrocene substitution patterns. The acetal protecting groups of 2,2'-bis-(acetal)-1,1'-diphenylphosphinoferrocene were removed to produce 1,1'-bis-carboxaldehyde-2,2'-diphenylphosphinoferrocene (4). The Cp rings of 1,1'-bisacetalferrocene were also further derivatised at the 2,2' positions with a silane to produce the ring-locked 1,1'-siloxane-2,5'-bisacetalferrocenophane (7). The acetal protecting groups were removed from this to produce 1,1'-siloxane-2,5'- ferrocenophanecarboxaldehyde (8). For both the phosphine and siloxane electrophiles, the substitution on the Cp rings gives chiral products (obtained as racemic mixtures). Due to the highly regioselective nature of the reaction and diastereoselectivity in the products only C(2)-symmetric compounds were observed without the presence of meso diastereoisomers. Subsequent ring-locking forced the Cp rings to rotate, leading to 1,1'-ring-locked ferrocenes with 2,5'-arrangement of the acetal groups (i.e. on opposite faces of the ferrocene unit).

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Published date: 1 June 2009
Keywords: 1, 1? 2, 5?-ferrocene derivatives, ortholithiation, ferroceneophane, ring-locked, regiospecific, chiral
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

Identifiers

Local EPrints ID: 346380
URI: http://eprints.soton.ac.uk/id/eprint/346380
ISSN: 0022-328X
PURE UUID: 52ccc976-ed13-471a-ae51-2ae2e0b59e7b
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 18 Dec 2012 16:58
Last modified: 15 Mar 2024 03:01

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Contributors

Author: Arthur Connell
Author: Peter J. Holliman
Author: Ian R. Butler
Author: Louise Male
Author: Simon J. Coles ORCID iD
Author: Peter N. Horton
Author: William Clegg
Author: Luca Russo

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