A catalytic hydroesterification process using HCO 2 Na, Ru 3 (CO) 12 and alcohols for the preparation of ester modified polybutadienesChem. Commun.

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Authors
Woo-Jin Park, Chang-Hee Lee, Dong-Su Kim, Chul-Ho Jun
Year
2015
DOI
10.1039/C5CC05815E
Subject
Materials Chemistry / Electronic, Optical and Magnetic Materials / Chemistry (all) / Surfaces, Coatings and Films / Metals and Alloys / Ceramics and Composites / Catalysis

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Kim and C. Jun, Chem. Commun., 2015, DOI: 10.1039/C5CC05815E.

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This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1

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Received 00th January 20xx,

Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x www.rsc.org/

A Catalytic Hydroesterification Process Using

HCO2Na, Ru3(CO)12 and Alcohols for Preparing

Ester Modified Polybutadienes

Woo-Jin Park, §

Chang-Hee Lee, §

Dong-Su Kim and Chul-Ho Jun,*

A method for transition metal catalyzed modification of polybutadiene was developed. Specifically, reactions of polybutadiene with alcohols and sodium formate in the presence of Ru3(CO)12 and 2-pyridinemethanol produce ester derivatives of polybutadiene. By using this approach, selected ratios of mixed ester derivatives of polybutadiene can be produced by employing the corresponding ratio of alcohols.

Because of their broad utility, chemically modified polymers are of great interest to industrial chemists. [1]

Methods to generate these substances, especially those that utilize transition-metal catalyzed reactions of unsaturated polymers to introduce desired functional groups, have great significance. [2]

However, only a few catalytic methods for modification of unsaturated polymers have been developed thus far. Processes of this type include hydroformylation, [3] aminomethylation, [4] hydrocarboxylation, [5] hydrosilylation [6] and hydrogenation. [7]

We developed a reaction of polybutadiene with aldehydes or primary alcohols that involves Rh-catalyzed, chelationassisted hydroacylation. [2a-b, d-e]

In this process, which utilizes a

Rh(I)/2-aminopicoline catalytic system, vinyl groups in the polybutadiene skeleton are transformed into acyl groups.

Recently, many transition metal catalyzed hydroesterification methods, which transforms alkene to ester, have been developed. [8]

We also devised a new chelation-assisted hydroesterification reaction of alkenes, which employs sodium formate and alcohols along with a catalytic amount of

Ru3(CO)12 and 2-pyridinemethanol. This process converts alkenes to esters (Scheme 1a) [9] through a pathway in which decomposition of sodium formate generates carbon monoxide to be used for carbonyl source and NaOH serves as a catalyst for the transesterification step (Scheme 1b). In this process 2pyridinemethanol is transformed to a pyridylmethyl ester intermediate through Ru(0) promoted carbonylation and alkene insertion, which then undergoes transesterification with the alcohol substrate to give the ester product.

Background of our idea

This work: multichemical modif ication of polybutadiene

R'+

Ru3(CO)12

R

O

C

O

R'R-OH + 2-pyridinemethanol

OH

RCO ONa

H

Ru3(CO)12 2-pyridinemethanol

C

O

NaO H y

I

C

O O

R

Ph

Ph zx

Ph y

I

Ph z +

CO

NaOH + for transesterif ication carbony l source

OH

R'

C

O O

R' (a) (c) (b) N [Ru]

C

OH

ON

OH [(CO)Ru] [Ru]

NaO

C

H

O

CO

NaOH

R'

N [Ru]

C

O

O

N [Ru] O

C

O

N

O

C

O

R

O

C

O

R OH R O Na

NaOH

NaOH catalyzed transester if icat ion

R'

R'

R'

R'

Scheme 1. (a) Ru3(CO)12/2-pyridinemethanol catalyzed hydroesterification of alkenes with sodium formate and alcohols (b) Proposed mechanism of hydroesterification reaction involving NaOH catalyzed transesterification step (c)

Multichemical modification of polybutadiene

In our continuing studies in this area, we utilized this alkene hydroesterification process to transform polybutadiene to ester tethered analogs (Scheme 1c). In addition, we showed that the new protocol can be applied to form multiple ester modified polybutadienes where the ester ratio can be controlled by regulating the quantities of two or more alcohol starting materials. Observations made in this study are described below.

Page 1 of 4 ChemComm

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D ow nl oa de d by

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N o n 12 /0 8/ 20 15 0 3: 17 :3 9.

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DOI: 10.1039/C5CC05815E

COMMUNICATION Journal Name 2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

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Table 1. Optimization of the carbonyl source in the hydroesterification process a a

All reactions were carried out with 1 (0.416 mmol of vinyl group), 2 (0.832 mmol), 3a (0.499 mmol), 4a (5 mol%) and 5a (20 mol%) in 1 mL of 1,4-dioxane. b 38% vinyl group is reduced or isomerized. c 56% vinyl group is reduced or isomerized. d 47% vinyl group is reduced or isomerized. e

Incorporation rate of ester group was calculated based on terminal phenyl in 6 and calculated as: 100 X w / (45, vinyl%). f

Isolated yields are based on modified polybutadiene.

In order to evaluate the efficiency of the polybutadiene hydroesterification methodology and to screen various formate as carbon monoxide sources, reactions of phenyl terminated polybutadiene (1), containing 45% vinyl and 55% internal olefin groups, with 2-phenylethyl alcohol (3a) were explored. Reaction of 1 with 3a at 150 o