Это может решить, что для вас:
(?:^|[^\\](?:\\\\)*)([a-zA-Z])\b
Демо Perl:
$ perl -ne 'print "-->$_<--\n" foreach m/(?:^|[^\\](?:\\\\)*)([a-zA-Z])\b/g'
5852& ^ \a\\b\\\\\c D \\e k.
-->b<--
-->D<--
-->e<--
-->k<--
o\a\\b\\\c\\\\d
-->o<--
-->b<--
-->d<--
Регулярное выражение гласит:
(?: # begin non capturing group
^ # the beginning of input,
| # or
[^\\] # a character which is not a backslash, followed by
(?:\\\\)* # two backslashes, zero or more times
) # end non capturing group, followed by
([a-zA-Z]) # a letter, captured, followed by
\b # a word break