Table 1.

Summary of photo-induced approaches reported for on-DNA transformations.

Transformation	Employed Method	Substrate Scope	DNA Integrity Studies	Limitations	Ref
Decarboxylative alkylation of amino acids to on-DNA alkenes	Simple Photoredox	Broad: primary-, secondary-, and tertiary amino acids.	No	Restricted to activated alkenes, styrenes, or Michael acceptors	30
Csp2–Csp3 Cross-coupling of on-DNA aryl halides and DHPs/amino acids	Metallaphotoredox	Broad for secondary- and tertiary DHPs. Works well with NBoc-protected amino acids	Yes	Absence of non-stabilized primary radicals from DHPs. Restricted to NBoc protected amino acids	32
on-DNA Decarboxylative arylation	Metallaphotoredox	Works well with primary- and secondary amino acids	Yes	Restricted to NBoc protected AAs. Low yields with tertiary amino acids	55
Decarboxylative Giese addition of RAEs to on-DNA alkenes	EDA Complex	Secondary- and tertiary RAE	No	Scope limited to a few examples. No primary RAEs tested and only two functionalized DNA-HP used	56
Csp2–Csp3 Cross-coupling with alkyl bromides	Metallaphotoredox	Secondary- and primary alkyl bromides	Yes	No acyclic secondary examples	48
Csp2–Csp3 Cross-coupling with alkyl bromides	Metallaphotoredox	Secondary- and primary alkyl bromides	No	No acyclic secondary examples. On-DNA aryl bromides provide low yields	55
[2+2] Cycloaddition using cinnamate esters	Energy Transfer	Broad	Yes	No limitation	57
on-DNA Synthesis of 1,2-amino alcohols	Simple Photoredox	Works with on-DNA aldehydes and moderately well with ketones	Yes	Low yield with ketones	58
Csp2–Csp3 Cross-coupling of on-DNA aryl halides with carboxylic acids	Metallaphotoredox	Works well with secondary cyclic carboxylic acids	Yes	No tertiary carboxylic acid or acyclic secondary examples. In general, moderate yields	59
C–H Functionalization of N-Boc heterocycles	Photoredox + HAT	5–6 Membered rings	Yes	Restricted to 4-substituted piperidine; good with EWG but moderate with EDG	60
Derivatization of quinoxalin-2-ones	Simple Photoredox	Broad, primary-, secondary-, and tertiary amino acids and aliphatic acids	Yes	Scope limited to a few primary amino acids and aliphatic acids. Limited to N-Boc amino acids	61
C–H Functionalization of I-aryl tertiary amines	Simple Photoredox	Broad, N-aryl tertiary amines	Yes	Only N-arylamines, poor reactivity with N-carbamate or N-alkylamines	62
on-DNA Sulfonylation and selenation	EDA Complex	Broad scope of sulfinates and diselenides	Yes	Few examples of heterocyclic-based compounds.	63
Hydroarylation of functionalized olefins	EDA Complex	Broad	Yes	No limitation	64
C–H Arylation of heteroarenes	Simple Photoredox	Broad	Yes	No limitation	49
Deaminative alkylation	Simple Photoredox	Secondary- and tertiary examples	Yes	Not very high yield, not very broad scope, no primary	54
Hydroalkylation of alkenes – BCP	Simple Photoredox	Broad, many examples	Yes	No limitation	50
C−H sulfonylation of arenes	EDA Complex	electron-rich and electron-poor sulfinates	Yes	Scope limited to few DNA-encoded thianthrenium salts	65