. 2023 Jun 29;145(27):14756–14765. doi: 10.1021/jacs.3c03253

Table 1. Fluoroalcohol/Base-Mediated ROP of Cyclic Monomers^a.

entry	mon.	feed ratio^b [I]\[M]\[base]\[TU4]	base	FA	co-solvent	time (min)	conv. (%)	M_n,theo^ckg mol^–¹	M_n,NMR^dkg mol^–¹	Đ^e
1	GL	1:40:1:0	^tBuP₁		DCM	3	>99	4.6	3.8	1.61
2	GL	1:40:1:0	^tBuP₂	HFIP		10	95.5	4.4	1.1ⁱ	1.28
3	GL	1:40:1:0	^tBuP₁	HFAB	DCM	10	98.8	4.6	4.6	1.22
4	GL	1:40:1:0	^tBuP₁	HFIB	DCM	5	96.4	4.5	3.3	1.37
5	GL	1:40:1:0	^tBuP₁	HFPP	DCM	5	>99	4.6	4.6	1.27
6	GL	1:40:1:0	TMG	HFAB	DCM	5	84.2	3.7	3.7	1.27
7	GL	1:40:1:0	DIEA	HFAB	DCM	5	>99	4.6	4.7	1.23
8	GL	1:40:1:0	^tBuP₁	HFAB	toluene	5	97.9	4.5	4.4	1.20
9	GL	1:40:1:0	^tBuP₁	HFAB	benzene	5	89.7	4.2	4.3	1.21
10	GL	1:40:1:2	^tBuP₁	HFAB	toluene	10	78.9	3.7	3.7	1.16
11	GL	1:40:1:2	^tBuP₂	HFAB	toluene	5	>99	4.6	3.9	1.15
12^f	GL	1:40:1:2	^tBuP₂	HFAB	toluene	5	>99	3.7	3.5	1.13
13	GL	1:80:1:2	^tBuP₂	HFAB	toluene	15	>99	9.4	9.8	1.08
14	GL	1:200:1:2	^tBuP₂	HFAB	toluene	30	>99	23.2	18.8	1.10
15	GL	1:500:1:2	^tBuP₂	HFAB	toluene	360	>99	58.0	55.4	1.19
16^g	LA	1:40:1:0	^tBuP₂	HFAB	toluene	24 h	93.7	5.3	5.3	1.09
17^g	VL	1:50:1:0	^tBuP₂	HFAB	toluene	24 h	61.8	3.0	3.0	1.07
18^h	PO	1:80:1:3	^tBuP₂	HFAB	toluene	24 h	>99	4.7	1.6ⁱ	1.05
19^h	EO	1:120:1:3	^tBuP₂	HFAB	toluene	1 h	>99	5.3	1.7ⁱ	1.05

All reactions were carried out at room temperature unless otherwise stated. [GL]₀ = 0.5 M, [LA]₀ = 1.0 M, [VL]₀ = 4.6 M, [PO]₀ = 6.3 M, and [EO]₀ = 9.0 M.

Molar feed ratio.

Determined by ([M]₀/[ini]₀) × M_w(M) × conv. % + M_w(I).

M_n,NMR was determined by ¹H NMR spectroscopy.

Đ was determined by SEC at 40 °C in HFIP as the eluent with poly(methyl methacrylate) standards.

Ethyl 2-hydroxyacetate (EthylGL) was used as the initiator.

Performed at 45 °C.

Triethylborane (Et₃B) was used⁶⁰ instead of TU4.

ⁱ

Initiated from solvent.

Table 1. Fluoroalcohol/Base-Mediated ROP of Cyclic Monomersa.

Table 1. Fluoroalcohol/Base-Mediated ROP of Cyclic Monomers^a.