Y. Zhu, C. Romain, and C. K. Williams, Nature, vol.540, pp.354-362, 2016.

S. Slomkowski, . Penczek, . S. Adv, T. Taguchi, H. Iwata et al., Poly(hydroxyalkanoate)s in, Polymer Science: A comprehensive Reference, vol.107, pp.157-82, 2012.

J. Sequence-controlled-polymers and . Ed, , 2018.

O. Dechy-cabaret, B. Martin-vaca, D. Bourissou-;-b, ). P. Dubois, O. Coulembier et al., Handbook of Ring-Opening Polymerization, For leading reviews on metal-catalyzed ROP of cyclic esters, vol.104, pp.486-494, 2004.

. Chem-;-f)-a, C. M. Buchard, J. Bakewell, C. K. Weiner, and T. Williams, , vol.2, pp.520-527, 2011.

). S. Guillaume, E. Kirillov, Y. Sarazin, and J. , Organomet. Chem, vol.39, pp.175-224, 2012.

. Carpentier, Chem. Eur. J, vol.21, pp.7988-8003, 2015.

D. M. Lyubov, A. O. Tolpygin, and A. A. Trifonov, Coord. Chem. Rev, vol.392, pp.83-145, 2019.

T. M. Ovitt, G. W. Coates, ;. Zhong, P. J. Dijkstra, and J. , For selected references in the isoselective ROP of rac-LA, see: Aluminum a), vol.124, 1316.

. Feijen, Angew. Chem. Int. Ed, vol.41, pp.4510-4513, 2002.

. Angew and . Chem, , vol.114, pp.4692-4695, 2002.

). N. Nomura, R. Ishii, Y. Yamamoto, and T. Kondo, Chem. Eur. J, vol.13, pp.4433-4451, 2007.

P. Hormnirun, E. L. Marshall, V. C. Gibson, R. I. Pugh, and A. J. White, Proc. Nat. Acad

;. A. Sci, K. Pilone, I. Press, M. Goldberg, M. Kol et al., 2940?2943; i), J. Am. Chem. Soc, vol.103, pp.15343-15348, 2006.

B. O. Douglas, P. Patrick, and . Mehrkhodavandi, Angew. Chem. Int. Ed, vol.47, pp.2290-2293, 2008.

. Angew, J. M. Chem-;-b)-d.-c.-aluthge, P. Ahn, ;. Mehrkhodavandi, A. J. Myers et al., 5284?5292; d), Chem. Sci, vol.120, 2008.

K. Williams, A. Chem, ;. H. Int, H. Wang, ). S. Ma-;-b et al., 689?692; c), Macromolecules, vol.56, pp.7911-7919, 2013.

M. Scha?fer, L. H. Thomas, M. F. Mahon, T. J. Woodman, J. P. Lowe-;-p et al., Chem. Sci, vol.6, pp.5034-5039, 2015.

C. Blake, ;. Wilson, T. P. Bakewell, N. Cao, X. F. Long et al., Angew. Chem. Int. Ed, vol.47, pp.6122-6125, 2008.

J. Williams, . Am, A. J. Bakewell, and N. White, Chem. Soc, vol.134, 2012.

J. Long, C. K. Williams-;-d, ). Xu, G. Yang, C. Liu et al., Alkaline earths: a) A. Harinath, Angew. Chem. Int. Ed, vol.53, pp.9380-9384, 2014.

K. Panda-;-b, ). J. Hu, C. Kan, H. Wang, and H. Ma, Macromolecules, vol.57, pp.5403-5312, 2018.

P. Robert, X. Haquette, L. Trivelli, V. Chamoreau, I. Guérineau et al., , vol.131, pp.12715-12719

C. X. Cai, A. Amgoune, C. W. Lehmann, and J. Carpentier, 330-331; b) For an account, see, Organometallics, vol.34, pp.4175-4189, 2004.

J. W. Kramer, D. S. Treitler, E. W. Dunn, P. M. Castro, T. Roisnel et al., J. Am. Chem. Soc, vol.131, pp.16042-16044, 2009.

Z. Zhuo, C. Zhang, Y. Luo, Y. Wang, Y. Yao et al., Chem. Commun, vol.54, pp.11998-12001, 2018.

A. Amgoune, C. M. Thomas, S. Ilinca, T. Roisnel, and J. Carpentier, Angew. Chem. Int. Ed, vol.45, pp.2782-2784, 2006.

, Angew. Chem, vol.118, pp.2848-2850, 2006.

R. Ligny, M. M. Hänninen, S. M. Guillaume, and J. Carpentier, Chem. Commun, vol.54, pp.8024-8031, 2018.

, Such beneficial non-covalent interactions (NCIs) have also been proposed on the basis of DFT computations in rac-LA ROP promoted by Zn-?-diketiminate complexes

L. Marshall, V. C. Gibson, H. S. Rzepa, ;. S. Gesslbauer, R. Savela et al., 6048-6051. b) The benefit of NCIs via hydrogen bond donors to explain the high activity and stereoselectivity of a new family of Al-bis(cathecolato-amino) complexes in the ROP of rac-LA has recently been discussed; see, J. Am. Chem. Soc, vol.127, pp.7912-7920, 2005.

, In the former mechanism, a stereochemical error is propagated, while in the latter a correction occurs since the chirality of the catalytic active site directs the stereochemical events; this can be easily probed by 13 C NMR analysis of the polymers recovered, the ancillary ligand in the catalyst is chiral and overrides the influence of the polymer chain-end (CEM), vol.100, pp.15303-15308, 2000.

C. G. Jaffredo, Y. Chapurina, S. M. Guillaume, and J. Carpentier, Angew. Chem. Int. Ed, vol.53, pp.2687-2691, 2014.

. Angew, . G. Chem-;-c, and Y. Jaffredo, , vol.126, 2014.

E. Chapurina, J. Kirillov, S. M. Carpentier, and . Guillaume, Chem. Eur. J, vol.22, p.7629, 2016.

R. Ligny, M. M. Hänninen, S. M. Guillaume, and J. Carpentier, Angew. Chem. Int. Ed, vol.56, pp.10388-10393, 2017.

. Angew and . Chem, , vol.129, pp.10524-10529, 2017.

, The best isoselectivity in the ROP of racemic BL promoted by a molecular catalyst has been achieved with a Y-salan complex with Pm up to 0.77; see ref 8. b) Heterogeneous bis(borohydride)Nd surface species resulting from the grafting of Nd(BH4)3(THF)3 onto silica promotes the ROP of rac-BBL

G. Delevoye, C. Tricot, C. M. Dujardin, R. M. Thomas, ;. Gauvin et al., c) Some Cr catalysts provide PHB with a modest isoselective bias (Pm = ca. 0.65) and no control over molar masses; see: d), Chem. Commun, vol.46, pp.1032-1034, 2010.

P. Bernhart, B. Preishuber-pflügl, and . Rieger, Angew. Chem. Int. Ed, vol.47, pp.3458-3460, 2008.

. Angew, S. Chem-;-r.-reichardt, R. Vagin, A. K. Reithmeier, B. Ott et al., Macromolecules, vol.120, pp.3963-3971, 2008.

X. Tang and E. Y. Chen, 2345-2356; b) A patent was also filled claiming the possibility to extend this chemistry to higher diolides bearing higher alkyl (ethyl, etc), alkenyl and aryl substituents, and to access the corresponding isotactic PBHAs; see, Nature Commun, vol.9, p.211144, 2018.

M. Hong, E. Y. Chen-;-b, ). Zhu, E. M. Watson, J. Tang et al., Nature Chem, vol.8, pp.398-403, 2016.

, Chem. Int. Ed, vol.57, pp.12588-12563, 2018.

. Angew and . Chem, , vol.130, pp.12738-12742, 2018.

J. Ainara, X. Zhu, A. Tang, E. Y. Etxeberria, and . Chen, Nature Commun, vol.10, pp.3559-3565, 2019.

J. Zhu and E. Y. Chen, Angew. Chem. Int. Ed, vol.58, pp.1178-1182, 2019.

. Angew and . Chem, , vol.131, pp.1190-1194, 2019.

Q. Yin, L. Yin, H. Wang, and J. Cheng, Acc. Chem. Res, vol.48, pp.1777-1787, 2015.

B. M. Vaca, D. Bourissou, ;. Q. Acs-macro-lett, L. Yin, H. Yin et al., 792?798; b), For reviews on OCAs polymerization, vol.4, pp.4207-4219, 1777.

Y. Sun, Z. Jia, C. Chen, Y. Cong, Y. Mao et al., J. Am. Chem. Soc, vol.139, pp.10723-10732, 2017.

A. J. Chmura, M. G. Davidson, C. J. Frankis, M. D. Jones, M. D. Lunn-;-a et al., 1293?1295; b), Angew. Chem., Int. Ed, vol.46, 2007.

. Angew and . Chem, , vol.46, pp.2280-2283, 2007.

Q. Feng and R. Tong, J. Am. Chem. Soc, vol.139, pp.6177-6182, 2017.

Q. Feng, L. Yang, Y. Zhong, D. Guo, G. Liu et al., Nature Commun, vol.9, pp.1559-1561, 2018.

R. Ligny, S. M. Guillaume, and J. Carpentier, Chem. Eur. J, vol.25, pp.6412-6424, 2019.

R. Ligny, , 2018.